EP2454296B1 - Copolymers, their use as thickeners and method for producing the same - Google Patents
Copolymers, their use as thickeners and method for producing the same Download PDFInfo
- Publication number
- EP2454296B1 EP2454296B1 EP10730180.6A EP10730180A EP2454296B1 EP 2454296 B1 EP2454296 B1 EP 2454296B1 EP 10730180 A EP10730180 A EP 10730180A EP 2454296 B1 EP2454296 B1 EP 2454296B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- different
- alkyl
- hydrogen
- compound
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001577 copolymer Polymers 0.000 title claims description 90
- 239000002562 thickening agent Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 100
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 48
- 238000002360 preparation method Methods 0.000 claims description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 33
- 239000003599 detergent Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002537 cosmetic Substances 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 150000002431 hydrogen Chemical class 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 10
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- -1 1-Anthracenyl Chemical group 0.000 description 75
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
- 239000013256 coordination polymer Substances 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 17
- 235000019198 oils Nutrition 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 238000009472 formulation Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 13
- 239000000194 fatty acid Substances 0.000 description 13
- 229930195729 fatty acid Natural products 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 150000004665 fatty acids Chemical class 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 8
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 8
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 8
- 150000002314 glycerols Chemical class 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000006239 protecting group Chemical group 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 239000003093 cationic surfactant Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 239000003925 fat Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 150000002763 monocarboxylic acids Chemical class 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 239000002304 perfume Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 235000014510 cooky Nutrition 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 4
- 235000019197 fats Nutrition 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 210000004209 hair Anatomy 0.000 description 4
- LPTIRUACFKQDHZ-UHFFFAOYSA-N hexadecyl sulfate;hydron Chemical compound CCCCCCCCCCCCCCCCOS(O)(=O)=O LPTIRUACFKQDHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 0 CCC(CC(C1)OC(C)(C)N)(C1(CC)OC(C)(C)*(C)OC(C)(C)*)OC(C)(C)*OC(C)(C)* Chemical compound CCC(CC(C1)OC(C)(C)N)(C1(CC)OC(C)(C)*(C)OC(C)(C)*)OC(C)(C)*OC(C)(C)* 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- NFBAXHOPROOJAW-UHFFFAOYSA-N phenindione Chemical class O=C1C2=CC=CC=C2C(=O)C1C1=CC=CC=C1 NFBAXHOPROOJAW-UHFFFAOYSA-N 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- IGERFAHWSHDDHX-UHFFFAOYSA-N 1,3-dioxanyl Chemical group [CH]1OCCCO1 IGERFAHWSHDDHX-UHFFFAOYSA-N 0.000 description 2
- JPRPJUMQRZTTED-UHFFFAOYSA-N 1,3-dioxolanyl Chemical group [CH]1OCCO1 JPRPJUMQRZTTED-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 2
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- HZLCGUXUOFWCCN-UHFFFAOYSA-N 2-hydroxynonadecane-1,2,3-tricarboxylic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C(O)(C(O)=O)CC(O)=O HZLCGUXUOFWCCN-UHFFFAOYSA-N 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
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- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910003319 β-Na2Si2O5 Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
- C07C41/08—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only to carbon-to-carbon triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
- C07C43/16—Vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
- C08G83/004—After treatment of dendrimers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
Definitions
- the present invention relates to the use of copolymers of the invention as thickeners, for example in detergents or cleaners.
- the present invention relates to compounds (B) which are particularly suitable as a comonomer for the preparation of copolymer of the invention. Furthermore, the present invention relates to compounds which are particularly suitable for the synthesis of (co) polymers according to the invention.
- thickeners In order to adjust the viscosity in aqueous formulations, for example detergents and cleaners, in printing pastes or in personal care products and cosmetic preparations, thickeners (thickeners) are often used. Thickeners may be natural or synthetic thickeners. Known synthetic thickeners are in many cases ammonia-neutralized copolymers of acrylic acid with acrylamide, which contain small amounts of a doubly ethylenically unsaturated comonomer such as methylenebisacrylamide in copolymerized form.
- the white oil which is required for the synthesis of the thickener, is thus at least partially high in the respective synthetic thickeners and which remains in applications on fibrous materials such as textile and there lead to deteriorated fastness properties and a deteriorated grip can.
- the thickener by simply washing, which is not successful in the use of white oil-containing thickeners in many cases.
- Associative thickeners are water-soluble polymers and have surfactant-like hydrophobic constituents which are capable of interacting in a hydrophilic, especially aqueous medium both with themselves and with other hydrophobic substances, in particular to associate and form a network.
- the resulting associative network thickens or gels the medium.
- WO 99/65958 describes alkali-soluble thickeners comprising the reaction product of an unsaturated carboxylic acid, a monoethylenically unsaturated monomer and a hydrophobic alkoxylated macromonomer.
- the monoethylenically unsaturated monomer includes a methyl group; it is preferably methyl acrylate.
- ethylenically unsaturated mono- or dicarboxylic acid (A) are, for example, mono- and polyethylenically unsaturated mono- or dicarboxylic acids, for example sorbic acid, and in particular monoethylenically unsaturated C 3 -C 10 -monocarboxylic acids, monoethylenically unsaturated C 4 -C 10 -dicarboxylic acids and their low molecular weight Anhydrides suitable.
- Suitable monoethylenically unsaturated C 4 -C 10 dicarboxylic acids and their low molecular weight anhydrides are itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride and mixtures of several of the abovementioned compounds.
- suitable monoethylenically unsaturated C 3 -C 10 -monocarboxylic acids are ethacrylic acid, (E) - and (Z) -crotic acid and preferably acrylic acid. Particularly preferred is methacrylic acid.
- mixtures of a monoethylenically unsaturated C 3 -C 10 -monocarboxylic acid and a monoethylenically unsaturated C 4 -C 10 -dicarboxylic acid or its anhydride are used, for example of (meth) acrylic acid and maleic anhydride.
- variable n may be an average value.
- Compound (B) may be a homopolymer, which may then also be called polymer (B). However, they are preferably copolymers, referred to for short as copolymers (B), selected from block copolymers, graft copolymers, alternating copolymers or preferably from random copolymers.
- Compound (B) can be prepared, for example, by ionic, for example anionic, or preferably by free-radical (co) polymerization of one or more (co) monomers, of which at least one has a structural unit of the general formula I.
- Structural units of the formula I can look, for example, as follows:
- compounds (B) are contaminated with products of incomplete reaction. Due to incomplete conversion, the following structural units can then be formed, for example:
- copolymers which, in addition to structural units of the general formula I, also have at least one structural unit which is attributable to the comonomer, with any free-radically polymerizable comonomers being suitable, for example vinylaromatics, in particular styrene, vinyl esters, in particular vinyl acetate, ethylenically unsaturated carboxylic acids, in particular (meth) acrylic acid, amides or esters of ethylenically unsaturated carboxylic acids, in particular C 1 -C 10 -alkyl esters of (meth) acrylic acid and (meth) acrylonitrile, furthermore maleic anhydride, halogen-containing comonomers such as vinyl chloride or vinylidene chloride and ⁇ -olefins, for example 1-decene, 1-hexene, isobutene or 1-dodecene.
- any free-radically polymerizable comonomers being suitable, for example vinylaromatics
- R 3 is methyl, and R 2 and R 4 are each hydrogen.
- R 2 , R 3 and R 4 are each hydrogen.
- R 2 and R 3 are each hydrogen, and R 4 is COOM.
- compound (B) has a molecular weight M w in the range of 200 to 100,000 g / mol, preferably 1,000 to 10,000 g / mol, particularly preferably 5,000 g / mol, determined for example by gel permeation chromatography (GPC).
- M w molecular weight in the range of 200 to 100,000 g / mol, preferably 1,000 to 10,000 g / mol, particularly preferably 5,000 g / mol, determined for example by gel permeation chromatography (GPC).
- compound (B) has a Fikentscher K value in the range of 8 to 40, measured at 23 ° C in THF / water mixtures, preferably in 2 wt% THF in water.
- compound (B) has a polydispersity M w / M n in the range from 1 to 4, preferably from 1.1 to 2, and more preferably in the range from 1.1 to 1.5.
- compound (B) has a hydroxyl number in the range from 1 to 270, preferably 5 to 10, particularly preferably 10 to 70 mg KOH / g, determined according to DIN 53240.
- the copolymer according to the invention has a molecular weight M w in the range from 1,000 to 10,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, more preferably 50,000 to 500,000 g / mol, determined, for example, by gel permeation chromatography (GPC).
- M w molecular weight in the range from 1,000 to 10,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, more preferably 50,000 to 500,000 g / mol, determined, for example, by gel permeation chromatography (GPC).
- the copolymer according to the invention has a polydispersity M w / M n in the range from 1 to 10.
- the molar ratio of structural units of the formula I to structural units of the formula II in the copolymer according to the invention is in the range from 0.01 to 10, preferably 0.05 to 2 and particularly preferably 0.1 to 0.5.
- Copolymers of the invention additionally comprise at least one further comonomer (C) in copolymerized form
- Suitable comonomers are ethylenically unsaturated compounds which can be copolymerized free-radically with the comonomers (A) and (B).
- Examples include: C 1 -C 10 alkyl esters of ethylenically unsaturated mono- or dicarboxylic acids, in particular of (meth) acrylic acid, vinyl acetate, vinylaromatics, in particular styrene and ⁇ -methylstyrene, ⁇ -olefins, in particular C 12 -C 20 - ⁇ Olefins, furthermore vinyl chloride, acrylonitrile and N-vinylpyrrolidone.
- C 1 -C 10 alkyl esters of ethylenically unsaturated mono- or dicarboxylic acids in particular of (meth) acrylic acid, vinyl acetate, vinylaromatics, in particular styrene and ⁇ -methylstyrene, ⁇ -olefins, in particular C 12 -C 20 - ⁇ Olefins, furthermore vinyl chloride, acrylonitrile and N-vinylpyrrolidone.
- C 1 -C 10 -alkyl esters of ethylenically unsaturated monocarboxylic acids are methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
- copolymer according to the invention comprises at least two different further comonomers (C) in copolymerized form.
- copolymer according to the invention contains exactly one further comonomer (C) in copolymerized form.
- Another object of the present invention is the use of copolymers of the invention as a thickener, in particular as associative thickener.
- copolymers of the invention have their property that they have a strongly pH-dependent solubility behavior in an aqueous medium.
- a further aspect of the present invention is accordingly the use of the copolymers according to the invention as an additive in detergents and cleaners and in cosmetic preparations.
- the subject matter furthermore relates to a process for the purification of textile substrates using the novel copolymers.
- Another object of the present invention are detergents and cleaners and cosmetic preparations containing at least one inventive copolymer.
- Detergents are primarily laundry detergents, while detergents are hard surfaces such as porcelain, ceramics, glass, stone, wood or concrete. Taking cosmetic preparations not only ointments, lotions, scrubs and other preparations which are directly suitable as cosmetic preparations, but also those preparations which are used as the basis for cosmetic consumer products.
- Copolymers of the invention can be used in the form of the free acids or in partially or completely neutralized form, for example partially or completely neutralized with ammonium, alkaline earth or, preferably, alkali metal cations. Copolymers of the invention are preferably used in unneutralized form, ie as free acid, and neutralized only immediately before or during the washing or cleaning process.
- Detergents and cleaners according to the invention or cosmetic preparations according to the invention can be in liquid or solid form.
- Solid detergent formulations according to the invention may be in powder, granule, extrudate or tablet form.
- Anionic surfactant is preferably added to the detergent in the form of salts.
- Suitable cations are e.g. Alkali metal ions such as sodium, potassium and lithium, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
- Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.
- Suitable bleach activators are e.g. N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methyl sulfate.
- TAED tetraacetylethylenediamine
- Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.
- Suitable color transfer inhibitors are, for example, homo-, co- and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine-N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.
- copolymers according to the invention and aqueous dispersions or solutions of copolymer according to the invention can be used as thickeners in hard surface cleaners.
- the present invention therefore relates to the use of copolymers according to the invention and of aqueous dispersions or solutions of copolymer according to the invention as additives for hard surface cleaners.
- Another object of the The present invention relates to hard surface cleaners containing the copolymer of the invention.
- Another object of the present invention is a process for the purification of hard surfaces using copolymer of the invention or aqueous dispersions or solutions of copolymer of the invention.
- Cleaners for hard surfaces include, for example, cleaners for metal, plastic, glass and ceramic cleaning, floor cleaners, sanitary cleaners, all-purpose household and commercial cleaners, technical cleaners (for use in car washes or high-pressure cleaners), cold cleaners, dishwashing detergents, rinse aids , Disinfectant cleaners, cleaners for the food and beverage industry, especially as bottle cleaners, as CIP cleaners (cleaning-in-place) in dairies, breweries and other establishments understood by food manufacturers.
- Cleaners containing copolymer of the invention are particularly suitable for cleaning hard surfaces such as glass, plastic and metal.
- the cleaners can be alkaline, acidic or neutral. They usually contain one or more surfactants in amounts of about 0.2 to 50 wt .-%.
- Alkaline cleaners may include soda, potash, sodium bicarbonate, potassium bicarbonate, sodium sesquicarbonate, potassium sesquicarbonate, sodium hydroxide, potassium hydroxide, amine bases such as monoethanolamine, diethanolamine, triethanolamine, ammonia or silicate in amounts up to 60% by weight, in some cases even up to 80%. -%.
- Hard surface cleaners according to the invention may also contain citrates, gluconates or tartrates in amounts of up to 80% by weight.
- Hard surface cleaners of the present invention may be in solid or liquid form.
- copolymer of the invention is contained in hard surface cleaners according to the invention in amounts of from 0.1 to 20, preferably from 0.2 to 15,% by weight.
- Cosmetic preparations according to the invention can be used, for example, for the care of skin, hair, cornea, fingernails or toenails or for oral care.
- Cosmetic preparations according to the invention can be present as aqueous or aqueous-alcoholic solutions, as O / W or W / O emulsions.
- cosmetic preparations according to the invention are in the form of shampoos, creams, foams, sprays (pump spray or aerosol), gels, gel sprays, lotions or mousses and can accordingly be formulated with conventional further auxiliaries.
- the cosmetic preparations according to the invention may be skin-cosmetic, hair-cosmetic, pharmaceutical, hygienic or pharmaceutical agents. Due to their film-forming properties, the copolymers described above are particularly suitable as additives for hair and skin cosmetics.
- Cosmetic preparations according to the invention are preferably in the form of a spray, a gel, a foam, an ointment, cream, an emulsion, a suspension, a lotion, a milk or a paste. If desired, liposomes or microspheres can also be used.
- oils and fats selected from low polarity hydrocarbons, such as mineral oils; linear saturated hydrocarbons, preferably having more than 8 carbon atoms, such as tetradecane, hexadecane, octadecane, etc., cyclic hydrocarbons, such as decahydronaphthalene, branched hydrocarbons; animal and vegetable oils, waxes, wax esters, petrolatum, esters, preferably esters of fatty acids, such as.
- low polarity hydrocarbons such as mineral oils
- linear saturated hydrocarbons preferably having more than 8 carbon atoms, such as tetradecane, hexadecane, octadecane, etc.
- cyclic hydrocarbons such as decahydronaphthalene, branched hydrocarbons
- animal and vegetable oils waxes, wax esters, petrolatum, esters, preferably esters of fatty acids, such as.
- esters of C 1 -C 40 monoalkanols with C 1 -C 22 monocarboxylic acids such as isopropyl isostearate, n-propyl myristate, isopropyl myristate, n-propyl palmitate, iso-propyl palmitate, hexacosanyl palmitate, octacosanyl palmitate, triacontanyl palmitate, dotriacontanyl palmitate, tetratriacontanyl palmitate, Hexancosanyl stearate, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriacontanyl stearate, salicylates such as C 1 -C 10 salicylates, e.g.
- Octyl salicylate benzoate esters such as C 10 -C 15 alkyl benzoates, benzyl benzoate, other cosmetic esters such as fatty acid triglycerides, Propylene glycol monolaurate, polyethylene glycol monolaurate, C 10 -C 15 alkyl lactates and mixtures thereof.
- silicone oils are z.
- linear polydimethylsiloxanes poly (methylphenylsiloxanes), cyclic siloxanes and mixtures thereof.
- the number average molecular weight of the polydimethylsiloxanes and poly (methylphenylsiloxanes) is preferably in a range of about 1,000 to 150,000 g / mol.
- Preferred cyclic siloxanes have 4- to 8-membered rings.
- Suitable cyclic siloxanes are, for. B. under the name cyclomethicone commercially available.
- Carrier preferred oil or fat components are selected from paraffin and paraffin oils, vaseline, natural fats and oils such as castor oil, soybean oil, peanut oil, olive oil, sunflower oil, sesame oil, avocado oil, cocoa butter, almond oil, peach kernel oil, castor oil, cod liver oil, lard, Spermacetöl, sperm oil, wheat germ oil, Macadamianussöl, evening primrose oil, jojoba oil, fatty alcohols such as lauryl, myristyl, cetyl, stearyl, oleyl, cetyl, fatty acids such as myristic, stearic, palmitic, oleic, linoleic, and various saturated, unsaturated and substituted fatty acids; Waxes, such as beeswax, carnauba wax, candililla wax, spermaceti and mixtures of the aforementioned oil or fat components.
- natural fats and oils such as castor oil, soybean oil, peanut oil, olive oil, sunflower
- cosmetic preparations according to the invention may comprise at least one component which is different from the carrier and inventive copolymer and is selected from cosmetically active care agents and active ingredients such as AHA acids, fruit acids, ceramides, phytantriol, collagen, vitamins and provitamins, for example vitamin A, E and C, retinol, bisabolol, parithenol, emulsifiers and co-emulsifiers, surfactants, preservatives, perfume oils, hair polymers, hair and skin conditioners, graft polymers, silicone compounds, water-soluble or dispersible silicone-containing polymers, natural and synthetic sunscreens, bleaches, gelling agents, Care products, colorants, dyes, pigments, micropigments such as titanium oxide or zinc oxide, opacifiers, tinting agents, tanning agents, bodying agents, moisturizers, re-fats, collagen, protein hydrolysates, lipids, antioxidants, Ent foaming agents, antistatics,
- cosmetically active care agents and active ingredients such as AHA
- Another object of the present invention are compounds (B).
- Compounds (B) according to the invention have at least one structural unit of the general formula I per molecule,
- compound (B) according to the invention has a molecular weight M w in the range from 200 to 100,000 g / mol, preferably up to 10,000 g / mol, particularly preferably up to 5,000 g / mol, determined for example by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- a suitable standard is, for example, polymethyl methacrylate (PMMA).
- compound (B) has a Fikentscher K value in the range of 8 to 40, measured at 23 ° C. in THF / water mixtures, preferably in 2% by weight solution in THF.
- compound (B) according to the invention has a polydispersity M n / M w in the range from 1 to 4, preferably from 1.1 to 2 and particularly preferably in the range from 1.1 to 1.5.
- At least one structural unit of the general formula I is a group of the formula III a or III b bonded to the backbone of copolymer of the invention.
- compound (B) according to the invention comprises at least one comonomer of the general formula IV a or IV b in copolymerized form, wherein R 5 is selected from methyl and hydrogen and the remaining variables are as defined above.
- compounds (B) according to the invention can be prepared as follows.
- at least one compound of the general formula R 1 - (OA 1 ) n -OH is reacted with glycerol or preferably a reactive derivative of glycerol, in particular with epichlorohydrin.
- glycerol or preferably a reactive derivative of glycerol, in particular with epichlorohydrin preferably a molar ratio of compound of the general formula R 1 - (OA 1 ) n -OH to reactive derivative of glycerol, in particular epichlorohydrin, such as 2: 1, it is desired to prepare compounds (B) which have structural units of general formula I. but where m> 1, it is then used further glycerol or another reactive derivative of glycerol.
- the preparation of compound of general formula VI or VI a can be carried out for example at temperatures in the range of 100 to 110 ° C.
- the preparation of compound of general formula VI a can also be carried out at temperatures below 100 ° C.
- Suitable catalysts are, for example, inorganic and organic bases.
- the base serves not only as a catalyst but also to neutralize the resulting HCl.
- Suitable inorganic bases are, for example, alkali metal carbonates and in particular alkali metal hydroxides such as NaOH and KOH.
- Suitable organic bases are, for example, tertiary amines, in particular triethylamine and [2,2,2] diazabicyclooctane (DABCO), and also pyridine and para-N, N-dimethylaminopyridine.
- Suitable solvents are, for example, ethers, in particular 1,4-dioxane, diisopropyl ether, tetrahydrofuran (“THF”) and di-n-butyl ether.
- ethers in particular 1,4-dioxane, diisopropyl ether, tetrahydrofuran (“THF”) and di-n-butyl ether.
- THF tetrahydrofuran
- Further suitable solvents are n-butyl acetate (“butyl acetate”), DMSO, N, N-dimethylformamide (“DMF”) and N-methylpyrrolidone and aromatic solvents such as toluene.
- a dehydrating agent for example molecular sieve, sodium sulfate, magnesium sulfate, or the water formed can be removed by azeotropic distillation.
- the reaction is carried out to give compounds of general formula VI over a period of 15 minutes to 48 hours, preferably 1 to 24 hours, more preferably 3 to 15 hours.
- the reaction to give the compound of general formula VI is carried out stepwise, in as many stages as it corresponds to the desired m.
- reactive derivative of glycerol, in particular epichlorohydrin in the number of stages is added.
- the stepwise reaction can be carried out by first reacting a certain amount of compound of the general formula R 1 - (OA 1 ) n -OH with half the number of moles of glycerol or preferably with a reactive derivative of glycerol, in particular with epichlorohydrin , Thereafter, an amount of glycerol or reactive derivative of glycerol is added, which corresponds to a quarter of the number of moles of compound of the general formula R 1 - (OA 1 ) n -OH, and converts.
- compound of the general formula VI can be reacted with a compound having an ethylenic double bond.
- reaction of compound of the general formula VI to give the compound of the general formula IV is carried out at temperatures in the range from -20 to + 70 ° C., preferably from +15 to 50 ° C.
- the reaction of compound of the general formula VI to give the compound of the general formula IV in a solvent or a mixture of solvents are, for example, ethers, in particular tetrahydrofuran, diethyl ether, 1,4-dioxane, acetone, or apolar solvents such as, for example, N, N-dimethylformamide (“DMF”), dimethylsulfoxide (DMSO) or hydrocarbons, for example cyclohexane.
- ethers in particular tetrahydrofuran, diethyl ether, 1,4-dioxane, acetone
- apolar solvents such as, for example, N, N-dimethylformamide (“DMF"), dimethylsulfoxide (DMSO) or hydrocarbons, for example cyclohexane.
- DMF N, N-dimethylformamide
- DMSO dimethylsulfoxide
- hydrocarbons for example cyclohexane
- Suitable catalysts are for example bases, for example sodium hydride and in particular tertiary amines such as N, N-dimethylaminopyridine. Catalysts are generally used in substoichiometric amounts. However, if it is desired to use an acid halide as the reactive acid derivative, it is possible to work with an excess of base, whereby the base can simultaneously neutralize the acid formed and serve as a catalyst.
- reaction of compound of the general formula VI to give the compound of the general formula IV is carried out over a period of 15 minutes to 12 hours, preference being given to 1 to 5 hours.
- one can react compound of the general formula VI with acetylene and obtains the compound according to the invention of formula IV a, where t zero and the remaining variables are as defined above.
- catalysts for the reaction with acetylene, it is possible to use one or more catalysts, preferably selected from basic catalysts. Especially suitable is KOH.
- the reaction with acetylene can be carried out with or without solvent.
- Suitable solvents are, for example, N-methylpyrrolidone, N-ethylpyrrolidone, toluene, xylene, THF and dioxane.
- the reaction with acetylene can be carried out, for example, at temperatures in the range from 80 to 160.degree. C., temperatures of around 120.degree. C., for example 110 to 130.degree. C., are preferred.
- the reaction with acetylene can be carried out at atmospheric pressure or preferably at elevated pressure, for example at 2 to 30 bar.
- the reaction with acetylene is carried out over a period of 15 minutes to 48 hours, preferably up to 36 hours.
- a diisocyanate for example TMXDI (tetramethylxylylene diisocyanate)
- the preparation of compounds of the formula IV b according to the invention can be carried out in the presence of a catalyst, for example in the presence of a tin-organic compound, in particular in the presence of DBTL (di-n-butyltin dilaurate).
- a catalyst for example in the presence of a tin-organic compound, in particular in the presence of DBTL (di-n-butyltin dilaurate).
- a solvent for example THF, 1,4-dioxane and di-n-butyl ether, furthermore acetone and nonpolar solvents, for example cyclohexane.
- the preparation of compounds of the formula IV b according to the invention can be carried out at a temperature in the range from 20 to 100.degree. C., preferably from 20 to 80.degree.
- the preparation of compounds of the formula IV b according to the invention can be carried out over a reaction time in the range from 1 to 10 hours, preferably 2 to 5 hours.
- R 1 is hydrogen
- a protective group as R 1 for example an acetate protecting group, which is split off in a later reaction step, for example under acidic aqueous conditions.
- Particularly preferred ketal protecting group is the isopropylidene protecting group.
- Another object of the provisional invention is a process for the preparation of copolymers according to the invention.
- Suitable initiators are in particular radical initiators, for example organic peroxides, in particular organic peroxides having at least one tert-butyl group or at least one tert-amyl group, and azo compounds, for example azobisisobutyronitrile (AIBN).
- redox initiators are suitable, for example Kombinbationen of hydrogen peroxide or sodium peroxodisulfate or one of the above mentioned peroxides with a reducing agent.
- Suitable reducing agents are, for example, ascorbic acid, tartaric acid, sodium bisulfite, potassium bisulfite, Fe (II) salts such as FeSO 4 or alkali metal salts of chelates of Fe (II).
- inorganic peroxides are suitable, for example potassium peroxodisulfate and sodium peroxodisulfate.
- the inventive production of copolymers according to the invention by copolymerization of compound of the general formula IV a and / or IV b can be carried out, for example, using at least one solvent.
- Suitable solvents may be, for example: N, N-dimethylformamide (DMF), dioxane, toluene or non-polar solvents such as cyclohexane.
- water is a suitable solvent. This is especially the case if one wishes to start the copolymerization according to the invention with inorganic peroxide.
- the copolymerization according to the invention is carried out without the use of a solvent.
- the concentration of the comonomer (s) at the beginning of the copolymerization according to the invention is from 60 to 95% by weight, preferably from 70 to 80% by weight of comonomer, based on all comonomers.
- the copolymerization according to the invention can also be carried out as bulk polymerization, ie without addition of solvent.
- the copolymerization according to the invention is carried out as emulsion polymerization.
- the copolymerization according to the invention can be carried out as a continuous process, as a semi-continuous process or in the form of a batch copolymerization.
- the (co) polymerization according to the invention is carried out at temperatures in the range from 60 to 90.degree.
- Another object of the present invention are compounds of general formula IV b
- compounds of the general formula IVa and IVb according to the invention are very well suited for preparing compounds (B) according to the invention. Their preparation succeeds, for example, according to the method described above.
- Emulsion E.3.1 was prepared, consisting of 220 g of completely desalinated water (demineralised water) 137.3 g of methacrylic acid (A.1) 155.3 g of ethyl acrylate (C.1) 164.4 g of n-butyl acrylate (C.2) 12.5 g of compound IV.1 (B.1) according to the invention 12.32 g of a 28 wt .-% aqueous solution of lauryl ether sulfate as emulsifier E-mul.1. 8.63 g of a 0.4% aqueous ascorbic acid solution
- Particle diameter The dispersion in question was diluted to 0.01% with water and the particle diameters were measured by light scattering in the "High Performance Particle Sizer 5001" (HPPS) from Malvern Instruments.
- LD value The dispersion in question was diluted with water to 0.01% and the light transmittance (LD) of the dispersion compared to pure water as a measure of the particle diameter optically measured in Hach DR / 2010.
- Table 1 Synthesis, composition and properties of copolymers CP.1 to CP.7 according to the invention (A.1) (B) (C.1) (C.2) emulsifier solid fuel O LT value each [pphm] [Wt .-%] [Nm] CP.1 29,25 1.25 (IV.1) 35.75 33.75 1.5 (Emul.1) 30.6 60 98 CP.2 29,25 0.75 (IV.2) 36.06 33.94 1.5 (Emul.1) 30.7 95 98 CP.3 28.2 2.5 (IV.1) 34.67 34.67 3.0 (Emul.2) 31.3 82 97 CP.4 29,25 1.25 (IV.1) 35.74 33.75 3.0 (Emul.2) 30.7 68 95 CP.5 29,25 1.
- copolymers according to the invention were stirred into stock formulations for liquid detergents according to Table 2 and the thickening effect was tested.
- the stock formulations were selected from the following stock formulations.
- the viscosity was measured taking into account the requirements of DIN 51550, DIN 53018, DIN 53019 with the Brookfield model RV-03 viscometer at a speed of 20 revolutions per minute with spindle no. 62 at 20 ° C.
- the viscosity of the non-thickened reference formulations can be seen in Tab. 1 Comparative Examples 1 to 3.
- the transmission of the non-thickened reference formulation and the liquid detergents according to the invention were in the same range between 97 and 100%. Addition of copolymers according to the invention caused no haze in the liquid detergent according to the invention.
Description
Die vorliegende Erfindung betrifft Copolymere, enthaltend als Comonomer einpolymerisiert
- (A) mindestens eine ethylenisch ungesättigte Mono- oder Dicarbonsäure,
- (B) mindestens ein (Co)polymer, das pro Molekül mindestens eine Struktureinheit der allgemeinen Formel I aufweist:
- R1
- verschieden oder gleich und gewählt aus Wasserstoff, C1-C30-Alkyl, C3-C10-Cycloalkyl, C6-C30-Aryl und C7-C30-Aralkyl,
- A1
- verschieden oder gleich und gewählt aus C2-C10-Alkylen, C6-C10-Arylen und C7-C10-Aralkylen,
- n
- verschieden oder gleich und gewählt aus null bis 200,
- m
- verschieden oder gleich und gewählt aus 1 bis 6,
- (C) mindestens ein weiteres Comonomer.
- (A) at least one ethylenically unsaturated mono- or dicarboxylic acid,
- (B) at least one (co) polymer which has at least one structural unit of the general formula I per molecule:
- R 1
- different or the same and selected from hydrogen, C 1 -C 30 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 30 -aryl and C 7 -C 30 -aralkyl,
- A 1
- different or the same and selected from C 2 -C 10 -alkylene, C 6 -C 10 -arylene and C 7 -C 10 -aralkylene,
- n
- different or equal and chosen from zero to 200,
- m
- different or equal and chosen from 1 to 6,
- (C) at least one other comonomer.
Weiterhin betrifft die vorliegende Erfindung die Verwendung von erfindungsgemäßen Copolymeren als Verdicker, beispielsweise in Wasch- oder Reinigungsmitteln.Furthermore, the present invention relates to the use of copolymers of the invention as thickeners, for example in detergents or cleaners.
Weiterhin betrifft die vorliegende Erfindung Verbindungen (B), die als Comonomer zur Herstellung von erfindungsgemäßen Copolymer besonders geeignet sind. Weiterhin betrifft die vorliegende Erfindung Verbindungen, die zur Synthese von erfindungsgemäßen (Co)polymeren besonders geeignet sind.Furthermore, the present invention relates to compounds (B) which are particularly suitable as a comonomer for the preparation of copolymer of the invention. Furthermore, the present invention relates to compounds which are particularly suitable for the synthesis of (co) polymers according to the invention.
Um in wässrigen Formulierungen, beispielsweise Wasch- und Reinigungsmitteln, in Druckpasten oder in Körperpflegemitteln und kosmetischen Zubereitungen die Viskosität einzustellen, verwendet man vielfach Verdicker (Verdickungsmittel). Bei Verdickern kann es sich um natürliche oder synthetische Verdicker handeln. Bekannte synthetische Verdicker sind in vielen Fällen mit Ammoniak neutralisierte Copolymere von Acrylsäure mit Acrylamid, die geringe Mengen eines zweifach ethylenisch ungesättigten Comonomers wie beispielsweise Methylenbisacrylamid einpolymerisiert enthalten.In order to adjust the viscosity in aqueous formulations, for example detergents and cleaners, in printing pastes or in personal care products and cosmetic preparations, thickeners (thickeners) are often used. Thickeners may be natural or synthetic thickeners. Known synthetic thickeners are in many cases ammonia-neutralized copolymers of acrylic acid with acrylamide, which contain small amounts of a doubly ethylenically unsaturated comonomer such as methylenebisacrylamide in copolymerized form.
Die Eigenschaften von bekannten Verdickern lassen sich noch verbessern.The properties of known thickeners can be improved.
Unerwünscht ist in vielen Fällen das Weißöl, welches für die Synthese der Verdicker erforderlich ist, sich somit zumindest anteilig hoch in den betreffenden synthetischen Verdickern befindet und das in Anwendungen auf faserigen Materialien wie beispielsweise Textil zurückbleibt und dort zu verschlechterten Echtheiten und zu einem verschlechterten Griff führen kann. Insbesondere dann, wenn man Druckpasten auf Basis von Dispersfarbstoffen (Dispersionsfarbstoffen) oder Reaktivfarbstoffen einsetzen möchte, ist es erwünscht, den Verdicker durch einfaches Waschen zu entfernen, was bei der Verwendung von Weißöl-haltigen Verdickern in vielen Fällen nicht gelingt.Unwanted is in many cases the white oil, which is required for the synthesis of the thickener, is thus at least partially high in the respective synthetic thickeners and which remains in applications on fibrous materials such as textile and there lead to deteriorated fastness properties and a deteriorated grip can. In particular, if you want to use printing pastes based on disperse dyes (disperse dyes) or reactive dyes, it is desirable to remove the thickener by simply washing, which is not successful in the use of white oil-containing thickeners in many cases.
Man hat auch versucht, das Weißöl nach der Synthese des Verdickers zu entfernten, beispielsweise durch Trocknung des Verdickers, insbesondere durch Sprühtrocknung. Man erhält dann so genannte Pulververdicker, die sich aber nicht stets in andere Formulierungen gut einrühren lassen.It has also tried to remove the white oil after the synthesis of the thickener, for example by drying the thickener, in particular by spray drying. One then obtains so-called powder thickeners, which however can not always be stirred well into other formulations.
Man hat versucht, die Nachteile des Weißöls durch die Verwendung von Assoziativerdickern zu umgehen. Assoziativverdicker sind wasserlösliche Polymere und haben tensidartige hydrophobe Bestandteile, welche in der Lage sind, sich in einem hydrophilen, insbesondere wässrigen Medium sowohl mit sich selbst als auch mit anderen hydrophoben Stoffen in Wechselwirkung zu treten, insbesondere zu assoziieren und ein Netzwerk zu bilden. Durch das resultierende assoziative Netzwerk wird das Medium verdickt oder geliert.Attempts have been made to circumvent the disadvantages of white oil by using associative thickeners. Associative thickeners are water-soluble polymers and have surfactant-like hydrophobic constituents which are capable of interacting in a hydrophilic, especially aqueous medium both with themselves and with other hydrophobic substances, in particular to associate and form a network. The resulting associative network thickens or gels the medium.
Bekannte Assoziativverdicker lassen sich jedoch noch verbessern. Insbesondere die Salzstabilität ist in vielen Fällen noch nicht ausreichend. Außerdem ist im Falle von Flüssigwaschmitteln in vielen Fällen eine verbesserte Transparenz wünschenswert, die einen besseren Verkaufserfolg ermöglicht.However, known associative thickeners can be improved. In particular, the salt stability is not sufficient in many cases. In addition, in the case of liquid detergents, in many cases improved transparency is desired, which allows a better sales success.
Es bestand also die Aufgabe, Waschmittel bereit zu stellen, die ein verbessertes Waschverhalten bei hohem Salzgehalt und eine verbesserte Transparenz aufweisen. Es bestand weiterhin die Aufgabe, Zusätze für Waschmittel bereit zu stellen, mit deren Hilfe sich die gewünschten Eigenschaften einstellen lassen. Es bestand weiterhin die Aufgabe, ein Verfahren zur Herstellung der betreffenden Zusätze bereit zu stellen. Dementsprechend wurden die eingangs definierten Copolymere gefunden, kurz auch als erfindungsgemäße Copolymere bezeichnet. Erfindungsgemäße Copolymere enthalten als Comonomere einpolymerisiert
- (A) mindestens eine ethylenisch ungesättigte Mono- oder Dicarbonsäure,
- (B) mindestens ein (Co)polymer, das unten näher beschrieben wird und das kurz auch als Verbindung (B) oder erfindungsgemäßes Verbindung (B) bezeichnet wird,
- (C) mindestens ein weiteres Comonomer.
- (A) at least one ethylenically unsaturated mono- or dicarboxylic acid,
- (B) at least one (co) polymer, which is described in more detail below and which is also referred to as compound (B) or compound (B) according to the invention,
- (C) at least one other comonomer.
Als ethylenisch ungesättigte Mono- oder Dicarbonsäure (A) sind beispielsweise mono- und mehrfach ethylenisch ungesättigte Mono- oder Dicarbonsäuren, beispielsweise Sorbinsäure, und insbesondere monoethylenisch ungesättigte C3-C10-Monocarbonäuren, monoethylenisch ungesättigte C4-C10-Dicarbonsäuren und ihre niedermolekularen Anhydride geeignet. Beispiele für geeignete monoethylenisch ungesättigte C4-C10-Dicarbonsäuren und ihre niedermolekularen Anhydride sind Itaconsäure, Citraconsäure, Mesaconsäure, Glutaconsäure, Aconitsäure, Maleinsäure, Fumarsäure, Maleinsäureanhydrid, Itaconsäureanhydrid und Mischungen von mehreren der vorstehend genannten Verbindungen. Beispiele für geeignete monoethylenisch ungesättigte C3-C10-Monocarbonäuren sind Ethacrylsäure, (E)- und (Z)-Crotonsäure und bevorzugt Acrylsäure. Besonders bevorzugt ist Methacrylsäure.As the ethylenically unsaturated mono- or dicarboxylic acid (A) are, for example, mono- and polyethylenically unsaturated mono- or dicarboxylic acids, for example sorbic acid, and in particular monoethylenically unsaturated C 3 -C 10 -monocarboxylic acids, monoethylenically unsaturated C 4 -C 10 -dicarboxylic acids and their low molecular weight Anhydrides suitable. Examples of suitable monoethylenically unsaturated C 4 -C 10 dicarboxylic acids and their low molecular weight anhydrides are itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride and mixtures of several of the abovementioned compounds. Examples of suitable monoethylenically unsaturated C 3 -C 10 -monocarboxylic acids are ethacrylic acid, (E) - and (Z) -crotic acid and preferably acrylic acid. Particularly preferred is methacrylic acid.
In einer Variante der vorliegenden Erfindung setzt man Mischungen von einer monoethylenisch ungesättigte C3-C10-Monocarbonäure und einer monoethylenisch ungesättigte C4-C10-Dicarbonsäure oder ihrem Anhydrid ein, beispielsweise von (Meth)acrylsäure und Maleinsäureanhydrid.In a variant of the present invention, mixtures of a monoethylenically unsaturated C 3 -C 10 -monocarboxylic acid and a monoethylenically unsaturated C 4 -C 10 -dicarboxylic acid or its anhydride are used, for example of (meth) acrylic acid and maleic anhydride.
Erfindungsgemäße Copolymere enthalten weiterhin mindestens ein Verbindung (B) einpolymerisiert. Verbindungen (B) weisen pro Molekül mindestens eine, beispielsweise im Mittel 1 bis 10 (Zahlenmittel), bevorzugt bis 5 und besonders bevorzugt bis 2 Struktureinheiten der allgemeinen Formel I auf,
- R1
- verschieden oder vorzugsweise gleich und gewählt aus Wasserstoff und bevorzugt C6-C30-Aryl, bevorzugt C6-C14-Aryl, beispielsweise Phenyl, 1-Naphthyl, 2-Naphthyl, 1-Anthracenyl, 2-Anthracenyl, 9-Anthracenyl, C7-C30-Aralkyl, bevorzugt Benzyl,
C3-C10-Cycloalkyl, substituiert oder unsubstituiert, bevorzugt Cyclopentyl, Cyclohexyl, Cyclooctyl, wobei ein oder mehrere nicht-benachbarte C-Atome durch Sauerstoff oder N-H oder N-CH3 ersetzt sein können, beispielhaft seien 1,3-Dioxolanyl, 1,3-Dioxanyl oder 13-Oxazolinyl genannt, bevorzugt sind 2,2-Dimethyl-1,3-dioxolanyl und 2,2-Dimethyl-1,3-dioxanyl genannt,
und insbesondere C1-C30-Alkyl, bevorzugt C1-C20-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl, n-Dodecyl, iso-Dodecyl, n-Tetradecyl, iso-Tetradecyl, n-Hexadecyl, iso-Hexadecyl, n-Octadecyl, iso-Octadecyl, n-Eicosyl, iso-Eicosyl. - A1
- verschieden oder vorzugsweise gleich und gewählt aus C6-C10-Arylen, beispielsweise ortho-Phenylen, meta-Phenylen, para-Phenylen, 1,6-Naphthylen, 1,7-Naphthylen, 2,6-Naphthylen, 2,7-Naphthylen oder 1,8-Naphthylen, C7-C10-Aralkylen wie beispielsweise -CH(C6H5)- oder -CH2-CH(C6H5)-,
und insbesondere aus C2-C10-Alkylen, substituiert oder vorzugsweise nicht substituiert, beispielsweise -CH2-, -CH(CH3)-, -CH(C2H5)-, -C(CH3)2-, -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, -CH(C2H5)-CH2-, -CH2-CH(C2H5)-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)8-, -(CH2)10-, bevorzugt -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, ganz besonders bevorzugt -CH2-CH2-, - n
- verschieden oder gleich und gewählt aus null bis 200, bevorzugt 1 bis 150, besonders bevorzugt 5 bis 50,
- m
- gewählt aus 1 bis 6, bevorzugt bis 4, besonders bevorzugt bis 2.
- R 1
- is preferably identical or different and selected from among hydrogen and preferably C 6 -C 30 -aryl, preferably C 6 -C 14 -aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, C 7 -C 30 -aralkyl, preferably benzyl,
C 3 -C 10 -cycloalkyl, substituted or unsubstituted, preferably cyclopentyl, cyclohexyl, cyclooctyl, where one or more nonadjacent carbon atoms may be replaced by oxygen or NH or N-CH 3 , by way of example 1,3-dioxolanyl, Called 1,3-dioxanyl or 13-oxazolinyl, preferably 2,2-dimethyl-1,3-dioxolanyl and 2,2-dimethyl-1,3-dioxanyl,
and in particular C 1 -C 30 -alkyl, preferably C 1 -C 20 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2- Ethylhexyl, n-nonyl, n-decyl, n-dodecyl, iso-dodecyl, n-tetradecyl, iso-tetradecyl, n-hexadecyl, iso-hexadecyl, n-octadecyl, isooctadecyl, n-eicosyl, iso-eicosyl. - A 1
- different or preferably identical and selected from C 6 -C 10 -aryls, for example ortho-phenylene, meta-phenylene, para-phenylene, 1,6-naphthylene, 1,7-naphthylene, 2,6-naphthylene, 2,7- Naphthylene or 1,8-naphthylene, C 7 -C 10 -aralkylenes such as -CH (C 6 H 5 ) - or -CH 2 -CH (C 6 H 5 ) -,
and in particular from C 2 -C 10 -alkylene, substituted or preferably unsubstituted, for example -CH 2 -, -CH (CH 3 ) -, -CH (C 2 H 5 ) -, -C (CH 3 ) 2 -, -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 3 ) -, -CH (C 2 H 5 ) -CH 2 -, -CH 2 -CH (C 2 H 5 ) -, - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 -, - (CH 2 ) 8 -, - (CH 2 ) 10 -, preferably -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 3 ) -, very particularly preferably -CH 2 -CH 2 -, - n
- different or the same and selected from zero to 200, preferably from 1 to 150, particularly preferably from 5 to 50,
- m
- selected from 1 to 6, preferably to 4, more preferably to 2.
Dabei kann es sich bei der Variable n um einen Mittelwert handeln.The variable n may be an average value.
Bei Verbindung (B) kann es sich um ein Homopolymer handeln, das dann auch Polymer (B) genannt werden kann. Vorzugsweise handelt es sich jedoch um Copolymere, kurz Copolymere (B) genannt, gewählt aus Blockcopolymeren, Pfropfcopolymeren, alternierenden Copolymeren oder vorzugsweise aus statistischen Copolymeren. Verbindung (B) kann man beispielsweise durch ionische, beispielsweise anionische, oder vorzugsweise durch radikalische (Co)polymerisation von einem oder mehreren (Co)monomeren herstellen, von denen mindestens eines eine Struktureinheit der allgemeinen Formel I aufweist.Compound (B) may be a homopolymer, which may then also be called polymer (B). However, they are preferably copolymers, referred to for short as copolymers (B), selected from block copolymers, graft copolymers, alternating copolymers or preferably from random copolymers. Compound (B) can be prepared, for example, by ionic, for example anionic, or preferably by free-radical (co) polymerization of one or more (co) monomers, of which at least one has a structural unit of the general formula I.
Struktureinheiten der Formel I können beispielsweise wie folgt aussehen:
In einer Ausführungsform der vorliegenden Erfindung sind Verbindungen (B) verunreinigt mit Produkten einer unvollständige Umsetzung. Aufgrund einer unvollständigen Umsetzung können dann beispielsweise folgende Struktureinheiten gebildet werden:
Für den Fall, dass man als Copolymer statistische Copolymere einzusetzen wünscht, kann man solche Copolymere einsetzen, die neben Struktureinheiten der allgemeinen Formel I noch mindestens eine Struktureinheit aufweisen, die auf das Comonomer zurückzuführen ist, wobei beliebige radikalisch polymerisierbare Comonomere geeignet sind, beispielsweise Vinylaromaten, insbesondere Styrol, Vinylester, insbesondere Vinylacetat, ethylenisch ungesättigte Carbonsäuren, insbesondere (Meth)acrylsäure, Amide oder Ester von ethylenisch ungesättigten Carbonsäuren, insbesondere C1-C10-Alkylester der (Meth)acrylsäure und (Meth)acrylnitril, weiterhin Maleinsäureanhydrid, halogenhaltige Comonomere wie beispielsweise Vinylchlorid oder Vinylidenchlorid und α-Olefine, beispielsweise 1-Decen, 1-Hexen, Isobuten oder 1-Dodecen.In the event that it is desired to use random copolymers as copolymer, it is possible to use those copolymers which, in addition to structural units of the general formula I, also have at least one structural unit which is attributable to the comonomer, with any free-radically polymerizable comonomers being suitable, for example vinylaromatics, in particular styrene, vinyl esters, in particular vinyl acetate, ethylenically unsaturated carboxylic acids, in particular (meth) acrylic acid, amides or esters of ethylenically unsaturated carboxylic acids, in particular C 1 -C 10 -alkyl esters of (meth) acrylic acid and (meth) acrylonitrile, furthermore maleic anhydride, halogen-containing comonomers such as vinyl chloride or vinylidene chloride and α-olefins, for example 1-decene, 1-hexene, isobutene or 1-dodecene.
Für den Fall, dass man als Copolymer statistische Copolymere einzusetzen wünscht, kann man solche Copolymere einsetzen, die neben Struktureinheiten der allgemeinen Formel I mindestens eine Struktureinheit der allgemeinen Formel II aufweisen,
- R2, R3
- gleich oder verschieden und gewählt aus C1-C6-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl; bevorzugt n-C1-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, besonders bevorzugt Methyl
und insbesondere Wasserstoff, - R4
- C1-C6-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl; bevorzugt n-C1-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, besonders bevorzugt Methyl
und insbesondere COOM oder Wasserstoff, - M
- gewählt aus Ammonium, substituiert wie beispielsweise Methylammonium, Dimethylammonium, Trimethylammonium, Ethanolammonium, oder vorzugsweise unsubstituiert, und insbesondere Wasserstoff und Metallkationen, beispielsweise Alkalimetallkationen wie Li+, Na+, K+, Rb+ oder Cs+, bevorzugt Na+ oder K+. M kann auch für ein halbes Äquivalent eines Erdalkalimetallkations stehen, beispielsweise für ein halbes Äquivalent Ca2+ oder Mg2+.
- R 2 , R 3
- identical or different and selected from C 1 -C 6 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl; preferably nC 1 -C 4 -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, particularly preferably methyl
and especially hydrogen, - R 4
- C 1 -C 6 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl; preferably nC 1 -C 4 -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, particularly preferably methyl
and in particular COOM or hydrogen, - M
- selected from ammonium, substituted such as methylammonium, dimethylammonium, trimethylammonium, ethanolammonium, or preferably unsubstituted, and in particular hydrogen and metal cations, for example alkali metal cations such as Li + , Na + , K + , Rb + or Cs + , preferably Na + or K + . M can also represent half an equivalent of an alkaline earth metal cation, for example, half a equivalent of Ca 2+ or Mg 2+ .
In einer Ausführungsform der vorliegenden Erfindung ist R3 Methyl, und R2 und R4 sind jeweils Wasserstoff.In one embodiment of the present invention, R 3 is methyl, and R 2 and R 4 are each hydrogen.
In einer Ausführungsform der vorliegenden Erfindung sind R2, R3 und R4 jeweils Wasserstoff.In one embodiment of the present invention, R 2 , R 3 and R 4 are each hydrogen.
In einer Ausführungsform der vorliegenden Erfindung sind R2 und R3 jeweils Wasserstoff, und R4 ist COOM.In one embodiment of the present invention, R 2 and R 3 are each hydrogen, and R 4 is COOM.
In einer Ausführungsform der vorliegenden Erfindung weist Verbindung (B) ein Molekulargewicht Mw im Bereich von 200 bis 100.000 g/mol auf, bevorzugt 1.000 bis 10.000 g/mol, besonders bevorzugt bis 5.000 g/mol, bestimmt beispielsweise durch Gelpermeationschromatograhie (GPC).In one embodiment of the present invention, compound (B) has a molecular weight M w in the range of 200 to 100,000 g / mol, preferably 1,000 to 10,000 g / mol, particularly preferably 5,000 g / mol, determined for example by gel permeation chromatography (GPC).
In einer Ausführungsform der vorliegenden Erfindung weist Verbindung (B) einen K-Wert nach Fikentscher im Bereich von 8 bis 40 auf, gemessen bei 23°C in THF/Wasser-Gemischen, vorzugsweise in 2 Gew.-% THF in Wasser.In one embodiment of the present invention, compound (B) has a Fikentscher K value in the range of 8 to 40, measured at 23 ° C in THF / water mixtures, preferably in 2 wt% THF in water.
In einer Ausführungsform der vorliegenden Erfindung weist Verbindung (B) eine Polydispersität Mw/Mn im Bereich von 1 bis 4 auf, bevorzugt von 1,1 bis 2 und besonders bevorzugt im Bereich von 1,1 bis 1,5.In one embodiment of the present invention, compound (B) has a polydispersity M w / M n in the range from 1 to 4, preferably from 1.1 to 2, and more preferably in the range from 1.1 to 1.5.
In einer Ausführungsform der vorliegenden Erfindung weist Verbindung (B) eine Hydroxylzahl im Bereich von 1 bis 270, bevorzugt 5 bis 10, besonders bevorzugt 10 bis 70 mg KOH/g auf, bestimmt nach DIN 53240.In one embodiment of the present invention, compound (B) has a hydroxyl number in the range from 1 to 270, preferably 5 to 10, particularly preferably 10 to 70 mg KOH / g, determined according to DIN 53240.
In einer Ausführungsform der vorliegenden Erfindung weist erfindungsgemäßes Copolymer ein Molekulargewicht Mw im Bereich von 1.000 bis 10.000.000 g/mol auf, bevorzugt 10.000 bis 1.000.000 g/mol, besonders bevorzugt 50.000 bis 500.000 g/mol, bestimmt beispielsweise durch Gelpermeationschromatograhie (GPC).In one embodiment of the present invention, the copolymer according to the invention has a molecular weight M w in the range from 1,000 to 10,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, more preferably 50,000 to 500,000 g / mol, determined, for example, by gel permeation chromatography (GPC).
In einer Ausführungsform der vorliegenden Erfindung weist erfindungsgemäßes Copolymer eine Polydispersität Mw/Mn im Bereich von 1 bis 10 auf.In one embodiment of the present invention, the copolymer according to the invention has a polydispersity M w / M n in the range from 1 to 10.
In einer Ausführungsform der vorliegenden Erfindung liegt das molare Verhältnis von Struktureinheiten der Formel I zu Struktureinheiten der Formel II in erfindungsgemäßem Copolymer im Bereich von 0,01 bis 10, bevorzugt 0,05 bis 2 und besonders bevorzugt 0,1 bis 0,5.In one embodiment of the present invention, the molar ratio of structural units of the formula I to structural units of the formula II in the copolymer according to the invention is in the range from 0.01 to 10, preferably 0.05 to 2 and particularly preferably 0.1 to 0.5.
In einer Ausführungsform der vorliegenden Erfindung ist mindestens eine Struktureinheit der allgemeinen Formel I über eine Gruppe der Formel III a
- X
- wird gewählt aus einer Einfachbindung, N-H und vorzugsweise Sauerstoff,
- t
- wird gewählt aus null und eins,
- w
- wird gewählt aus null und eins,
- A2
- wird gewählt aus C1-C50-Alkylen, substituiert oder vorzugsweise nicht substituiert, wobei eine oder mehrere nicht-benachbarte CH2-Gruppen durch Sauerstoff ersetzt sein können. Beispiele für geeignete Gruppen A2 sind C2-C10-Alkylen, bevorzugt -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, besonders bevorzugt -CH2-CH2-, weiterhin -CH2-CH2-O-, -CH(CH3)-CH2-O-, -CH2-CH(CH3)-O-, -[CH2-CH2-O-]y-, -[CH(CH3)-CH2-O-]y-, -[CH2-CH(CH3)-O-]y-, wobei y eine ganze Zahl im Bereich von 2 bis 20, bevorzugt 2 bis 15 und insbesondere 3 bis 10 ist.
- X
- is selected from a single bond, NH and preferably oxygen,
- t
- is chosen from zero and one,
- w
- is chosen from zero and one,
- A 2
- is selected from C 1 -C 50 alkylene, substituted or preferably unsubstituted, wherein one or more non-adjacent CH 2 groups may be replaced by oxygen. Examples of suitable groups A 2 are C 2 -C 10 -alkylene, preferably -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 3 ) -, more preferably -CH 2 -CH 2 -, furthermore -CH 2 -CH 2 -O-, -CH (CH 3 ) -CH 2 -O-, -CH 2 -CH (CH 3 ) -O-, - [CH 2 -CH 2 -O-] y -, - [CH (CH 3 ) -CH 2 -O-] y -, - [CH 2 -CH (CH 3 ) -O-] y -, where y is an integer in the range of 2 to 20, preferably 2 to 15 and in particular 3 to 10.
Erfindungsgemäße Copolymere enthalten weiterhin mindestens ein weiteres Comonomer (C) einpolymerisiert Geeignete Comonomere sind ethylenisch ungesättigte Verbindungen, die sich radikalisch mit den Comonomeren (A) und (B) copolymerisieren lassen. Beispielhaft sind zu nennen: C1-C10-Alkylester von ethylenisch ungesättigten Mono- oder Dicarbonsäuren, insbesondere von (Meth)acrylsäure, Vinylacetat, Vinylaromaten wie insbesondere Styrol und α-Methylstyrol, α-Olefine wie insbesondere C12-C20-α-Olefine, weiterhin Vinylchlorid, Acrylnitril und N-Vinylpyrrolidon. Bevorzugte Beispiele für C1-C10-Alkylester von ethylenisch ungesättigten Monocarbonsäuren sind Methyl(meth)acrylat, Ethyl(meth)acrylat, n-Butyl(meth)acrylat und 2-Ethylhexyl(meth)acrylat.Copolymers of the invention additionally comprise at least one further comonomer (C) in copolymerized form Suitable comonomers are ethylenically unsaturated compounds which can be copolymerized free-radically with the comonomers (A) and (B). Examples include: C 1 -C 10 alkyl esters of ethylenically unsaturated mono- or dicarboxylic acids, in particular of (meth) acrylic acid, vinyl acetate, vinylaromatics, in particular styrene and α-methylstyrene, α-olefins, in particular C 12 -C 20 -α Olefins, furthermore vinyl chloride, acrylonitrile and N-vinylpyrrolidone. Preferred examples of C 1 -C 10 -alkyl esters of ethylenically unsaturated monocarboxylic acids are methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäßes Copolymer mindestens zwei verschiedene weitere Comonomere (C) einpolymerisiert. In einer anderen Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäßes Copolymer genau ein weiteres Comonomer (C) einpolymerisiert.In one embodiment of the present invention copolymer according to the invention comprises at least two different further comonomers (C) in copolymerized form. In another embodiment of the present invention, copolymer according to the invention contains exactly one further comonomer (C) in copolymerized form.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäßes Copolymer einpolymerisiert:
- 0,1 bis 99 Gew.-%, bevorzugt 5 bis 70 Gew.-%, besonderes bevorzugt 10 bis 50 Gew.-% ethylenisch ungesättigte Mono- oder Dicarbonsäure (A),
- 0,001 bis 99 Gew.-%, bevorzugt 0,01 bis 50 Gew.-%, besonderes bevorzugt 0,1 bis 10 Gew.-% Verbindung (B),
- insgesamt 0.1 bis 99 Gew.-%, bevorzugt 5 bis 80 Gew.-%, besonderes bevorzugt 30 bis 60 Gew.-% weitere(s) Comonomer(e) (C).
- From 0.1 to 99% by weight, preferably from 5 to 70% by weight, particularly preferably from 10 to 50% by weight, of ethylenically unsaturated mono- or dicarboxylic acid (A),
- 0.001 to 99% by weight, preferably 0.01 to 50% by weight, particularly preferably 0.1 to 10% by weight of compound (B),
- in total from 0.1 to 99% by weight, preferably from 5 to 80% by weight, particularly preferably from 30 to 60% by weight, of further comonomer (s) (C).
Dabei sind Angaben in Gew.-% jeweils auf gesamtes erfindungsgemäßes Copolymer bezogen.In this case, data in% by weight are based in each case on the total copolymer of the invention.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen Copolymeren als Verdicker, insbesondere als Assoziativ-Verdicker. Dabei kommt erfindungsgemäßen Copolymeren ihre Eigenschaft zu Gute, dass sie ein stark pH-Wert abhängiges Löslichkeitsverhalten in wässrigem Milieu aufweisen. Ein weiterer Aspekt der vorliegenden Erfindung ist demgemäß die Verwendung der erfindungsgemäßen Copolymerisate als Zusatz in Wasch- und Reinigungsmitteln sowie in kosmetischen Zubereitungen. Gegenstand ist weiterhin ein Verfahren zur Reinigung von textilen Substraten unter Verwendung der erfindungsgemäßen Copolymerisate.Another object of the present invention is the use of copolymers of the invention as a thickener, in particular as associative thickener. In this case, copolymers of the invention have their property that they have a strongly pH-dependent solubility behavior in an aqueous medium. A further aspect of the present invention is accordingly the use of the copolymers according to the invention as an additive in detergents and cleaners and in cosmetic preparations. The subject matter furthermore relates to a process for the purification of textile substrates using the novel copolymers.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Wasch- und Reinigungsmittel sowie kosmetische Zubereitungen, enthaltend mindestens ein erfindungsgemäßes Copolymer. Dabei sind unter Waschmitteln hauptsächlich Waschmittel für Textil zu verstehen, während Reinigungsmittel harte Oberflächen wie beispielsweise Porzellan, Keramik, Glas, Stein, Holz oder Beton betreffen. Unter kosmetischen Zubereitungen sind nicht nur Salben, Lotions, Peelings und andere Zubereitungen, die sich unmittelbar als kosmetische Zubereitungen eignen, zu verstehen, sondern auch solche Zubereitungen, die als Basis für kosmetische Verbraucherprodukte verwendet werden.Another object of the present invention are detergents and cleaners and cosmetic preparations containing at least one inventive copolymer. Detergents are primarily laundry detergents, while detergents are hard surfaces such as porcelain, ceramics, glass, stone, wood or concrete. Taking cosmetic preparations not only ointments, lotions, scrubs and other preparations which are directly suitable as cosmetic preparations, but also those preparations which are used as the basis for cosmetic consumer products.
Erfindungsgemäße Copolymere können dabei in Form der freien Säuren oder in partiell oder vollständig neutralisierter Form eingesetzt werden, beispielsweise mit Ammonium-, Erdalkali- oder vorzugsweise Alkalimetallkationen partiell oder vollständig neutralisiert. Bevorzugt setzt man erfindungsgemäße Copolymere in nicht neutralisierter Form, also als freie Säure, ein und neutralisiert erst unmittelbar vor oder während des Wäsch- oder Reinigungsvorgangs.Copolymers of the invention can be used in the form of the free acids or in partially or completely neutralized form, for example partially or completely neutralized with ammonium, alkaline earth or, preferably, alkali metal cations. Copolymers of the invention are preferably used in unneutralized form, ie as free acid, and neutralized only immediately before or during the washing or cleaning process.
Erfindungsgemäße Wasch- und Reinigungsmittel bzw. erfindungsgemäße kosmetische Zubereitungen können in flüssiger oder fester Form vorliegen.Detergents and cleaners according to the invention or cosmetic preparations according to the invention can be in liquid or solid form.
Erfindungsgemäße feste Waschmittel enthalten vorzugsweise folgende Komponenten:
- (a) 0,05 bis 20 Gew.-% mindestens eines erfindungsgemäßen Copolymers,
- (b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids,
- (c) 0,5 bis 50 Gew.-% eines anorganischen Builders,
- (d) 0 bis 10 Gew.-% eines organischen Cobuilders und
- (e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe, wie Stellmittel, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Farbübertragungsinhibitoren, weitere Vergrauungsinhibitoren, Soil-Release-Polyester, Faser- und Farbschutzadditve, Silicone, Farbstoffe, Bakterizide, Auflösungsverbesserer und/oder Sprengmittel,
- (a) 0.05 to 20% by weight of at least one copolymer according to the invention,
- (b) 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant,
- (c) 0.5 to 50% by weight of an inorganic builder,
- (d) 0 to 10% by weight of an organic cobuilder and
- (e) 0 to 60% by weight of other conventional ingredients, such as sizing agents, enzymes, perfume, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, dye transfer inhibitors, other grayness inhibitors, soil release polyesters, fiber and color protective additives, silicones, dyes , Bactericides, dissolution improvers and / or disintegrants,
Erfindungsgemäße feste Waschmittelformulierungen können in Pulver-, Granulat-, Extrudat- oder Tablettenform vorliegen.Solid detergent formulations according to the invention may be in powder, granule, extrudate or tablet form.
Erfindungsgemäße flüssige Waschmittelformulierungen haben vorzugsweise folgende Zusammensetzung:
- (a) 0,05 bis 20 Gew.-% mindestens eines erfindungsgemäßen Copolymers,
- (b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids,
- (c) 0 bis 20 Gew.-% eines anorganischen Builders,
- (d) 0 bis 10 Gew.-% eines organischen Cobuilders,
- (e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe, wie Soda, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Farbübertragungsinhibitoren, weitere Vergrauungsinhibitoren , Soil-Release-Polyester, Faser- und Farbschutzadditve, Silicone, Farbstoffe, Bakterizide, organische Lösungsmittel, Löslichkeitsvermittler, Hydrotrope, Verdicker und/oder Alkanolamine und
- (f) 0 bis 99,45 Gew.-% Wasser.
- (a) 0.05 to 20% by weight of at least one copolymer according to the invention,
- (b) 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant,
- (c) 0 to 20% by weight of an inorganic builder,
- (d) 0 to 10% by weight of an organic cobuilder,
- (e) 0 to 60% by weight of other common ingredients such as soda, enzymes, perfume, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, dye transfer inhibiting agents, other grayness inhibitors, soil release polyesters, fiber and color protective additives, silicones, dyes , Bactericides, organic solvents, solubilizers, hydrotropes, thickeners and / or alkanolamines and
- (f) 0 to 99.45% by weight of water.
Als nichtionische Tenside (b) eignen sich dabei vor allem:
- Alkoxylierte C8-C22-Alkohole, wie Fettalkoholalkoxylate, Oxoalkohotalkoxylate und Guerbetalkoholalkoxylate: Die Alkoxylierung kann mit C2-C20 -Alkylenoxiden, vorzugsweise mit Ethylenoxid, Propylenoxid und/oder Butylenoxid erfolgen. Es können Blockcopolymerisate oder statistische Copolymere vorliegen. Pro mol Alkohol enthalten sie üblicherweise 1 bis 50 mol, vorzugsweise 1 bis 20 mol, mindestens eines Alkylenoxids. Besonders bevorzugtes Alkylenoxid ist Ethylenoxid. Die Alkohole haben vorzugsweise 10 bis 18 Kohlenstoffatome.
- Alkylphenolalkoxylate, insbesondere Alkylphenolethoxylate, die C6-C14-Alkylketten und 5 bis 30 mol Alkylenoxid/mol enthalten.
- Alkylpolyglucoside, die C8-C22-, vorzugsweise C10-C18-Alkylketten und in der Regel 1 bis 20, vorzugsweise 1,1 bis 5 Glucosideinheiten enthalten.
- N-Alkylglucamide, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate sowie Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid.
- Alkoxylated C 8 -C 22 -alcohols, such as fatty alcohol alkoxylates, oxo-alcohol-alkoxylates and guerbet-alcohol alkoxylates: The alkoxylation can be carried out using C 2 -C 20 -alkylene oxides, preferably with ethylene oxide, propylene oxide and / or butylene oxide. There may be block copolymers or random copolymers. They usually contain from 1 to 50 mol, preferably from 1 to 20 mol, of at least one alkylene oxide per mole of alcohol. Particularly preferred alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.
- Alkylphenolalkoxylate, especially alkylphenol ethoxylates containing C 6 -C 14 alkyl chains and 5 to 30 moles of alkylene oxide / mol.
- Alkylpolyglucosides containing C 8 -C 22 -, preferably C 10 -C 18 -alkyl chains and usually 1 to 20, preferably 1.1 to 5 glucoside units.
- N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.
Geeignete anionische Tenside sind beispielsweise:
- Sulfate von (Fett)alkoholen mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen, insbesondere C9-C11-Alkoholsulfate, C12-C14-Alkoholsulfate, C12-C18-Alkoholsulfate, Laurylsulfat, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat.
- Sulfatierte alkoxylierte C8-C22-Alkohole (Alkylethersulfate): Verbindungen dieser Art werden beispielsweise dadurch hergestellt, dass man zunächst einen C8-C22-, vorzugsweise einen C10-C18-Alkohol, z.B. einen Fettalkohol, alkoxyliert und das Alkoxylierungsprodukt anschließend sulfatiert. Für die Alkoxylierung verwendet man vorzugsweise Ethylenoxid.
- Lineare C8-C20-Alkylbenzolsulfonate (LAS), vorzugsweise lineare C9-C13-Alkylben-zolsulfonate und -Alkyltoluolsulfonate.
- Alkansulfonate, insbesondere C8-C24-, vorzugsweise C10-C18-Alkansulfonate.
- Seifen, wie die Na- und K-Salze von C8-C24-Carbonsäuren.
- Sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18 carbon atoms, in particular C 9 -C 11 -alcohol sulfates, C 12 -C 14 -alcohol sulfates, C 12 -C 18 -alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, Stearyl sulfate and tallow fatty alcohol sulfate.
- Sulfated alkoxylated C 8 -C 22 -alcohols (alkyl ether sulfates): compounds of this type are prepared, for example, by first alkoxylating a C 8 -C 22 -alcohol, preferably a C 10 -C 18 -alcohol, for example a fatty alcohol, and the alkoxylation product subsequently sulfated. For the alkoxylation is preferably used ethylene oxide.
- Linear C 8 -C 20 -alkylbenzenesulfonates (LAS), preferably linear C 9 -C 13 -alkylbenzenesulfonates and -alkyltoluenesulfonates.
- Alkanesulfonates, in particular C 8 -C 24 -, preferably C 10 -C 18 -alkanesulfonates.
- Soaps, such as the Na and K salts of C 8 -C 24 carboxylic acids.
Anionisches Tensid wird dem Waschmittel vorzugsweise in Form von Salzen zugegeben. Geeignete Kationen sind dabei z.B. Alkalimetallionen, wie Natrium, Kalium und Lithium, und Ammoniumsalze, wie Hydroxyethylammonium-, Di(hydroxyethyl)-ammonium- und Tri(hydroxyethyl)ammoniumsalze.Anionic surfactant is preferably added to the detergent in the form of salts. Suitable cations are e.g. Alkali metal ions such as sodium, potassium and lithium, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
Als besonders geeignete kationische Tenside seien genannt:
- C7-C25-Alkylamine;
- N,N-Dimethyl-N-(hydroxy-C7-C25-alkyl)ammoniumsalze;
- mit Alkylierungsmitteln quaternisierte Mono- und Di-(C7-C25-alkyl)dimethylammoniumverbindungen;
- Esterquats, insbesondere quaternäre veresterte Mono-, Di- und Trialkanolamine, die mit C8-C22-Carbonsäuren verestert sind;
- Imidazolinquats, insbesondere 1-Alkylimidazoliniumsalze der Formeln VI oder VII
- R6
- gleich oder verschieden und gewählt aus C1-C25-Alkyl oder C2-C25-Alkenyl;
- R7
- C1-C4-Alkyl oder Hydroxy-C1-C4-alkyl;
- R8
- C1-C4-Alkyl, Hydroxy-C1-C4-alkyl oder ein Rest R6-(CO)-Y-(CH2)p- (Y Sauerstoff oder -NH-; p: 2 oder 3),
wobei für den Fall, dass R8 gleich R6-(CO)-Y-(CH2)p- ist, mindestens ein Rest R6 für C7-C22-Alkyl steht.
- C 7 -C 25 -alkylamines;
- N, N-dimethyl-N- (hydroxy-C 7 -C 25 -alkyl) ammonium salts;
- mono- and di (C 7 -C 25 -alkyl) dimethylammonium compounds quaternized with alkylating agents;
- Esterquats, in particular quaternary esterified mono-, di- and trialkanolamines esterified with C 8 -C 22 -carboxylic acids;
- Imidazolinquats, in particular 1-Alkylimidazoliniumsalze of the formulas VI or VII
- R 6
- identical or different and selected from C 1 -C 25 alkyl or C 2 -C 25 alkenyl;
- R 7
- C 1 -C 4 -alkyl or hydroxy-C 1 -C 4 -alkyl;
- R 8
- C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl or a radical R 6 - (CO) -Y- (CH 2 ) p - (Y is oxygen or -NH-; p: 2 or 3),
wherein in the event that R 8 is R 6 - (CO) -Y- (CH 2 ) p -, at least one R 6 is C 7 -C 22 alkyl.
Als anorganische Builder eignen sich insbesondere:
- Kristalline und amorphe Alumosilikate mit ionenaustauschenden Eigenschaften, wie vor allem Zeolithe: Verschiedene Typen von Zeolithen sind geeignet, insbesondere die Zeolithe A, X, B, P, MAP und HS in ihrer Na-Form oder in Formen, in denen Na teilweise gegen andere Kationen wie Li, K, Ca, Mg oder Ammonium ausgetauscht ist,
- Kristalline Silikate, wie insbesondere Disilikate und Schichtsilikate, z.B. δ- und β-Na2Si2O5. Die Silikate können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden, bevorzugt sind die Na-, Li- und Mg-Silikate,
- Amorphe Silikate, wie Natriummetasilikat und amorphes Disilikat,
- Carbonate und Hydrogencarbonate: Diese können in Form ihrer Alkalimetall-, Erd-alkalimetall- oder Ammoniumsalze eingesetzt werden. Bevorzugt sind Na-, Li- und Mg-Carbonate und -Hydrogencarbonate, insbesondere Natriumcarbonat und/oder Natriumhydrogencarbonat,
- Polyphosphate, wie Pentanatriumtriphosphat.
- Crystalline and amorphous aluminosilicates with ion-exchanging properties, in particular zeolites: Various types of zeolites are suitable, in particular the zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na partially opposes other cations as Li, K, Ca, Mg or ammonium is exchanged,
- Crystalline silicates, in particular disilicates and sheet silicates, for example δ- and β-Na 2 Si 2 O 5 . The silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preference being given to the Na, Li and Mg silicates,
- Amorphous silicates, such as sodium metasilicate and amorphous disilicate,
- Carbonates and bicarbonates: These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to Na, Li and Mg carbonates and hydrogencarbonates, in particular sodium carbonate and / or sodium bicarbonate,
- Polyphosphates, such as pentasodium triphosphate.
Als organische Cobuilder eignen sich vor allem:
- Niedermolekulare Cärbonsäuren, wie Citronensäure, hydrophob modifizierte Citronensäure, z. B. Agaricinsäure, Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Bernsteinsäure, Imidodibernsteinsäure, Oxydibernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure, Alkyl- und Alkenylbernsteinsäuren und Aminopolycarbonsäuren, z.B. Nitrilotriessigsäure, β-Alanin-diessigsäure, Ethylendiaminte traessigsäure, Serindiessigsäure, Isoserindiessigsäure, N-(2-Hydroxyethyl)iminodiessigsäure, Ethylendiamindibernsteinsäure und Methyl- und Ethylglycindiessigsäure.
- Oligomere und polymere Carbonsäuren, wie Homopolymere von Acrylsäure und Asparaginsäure, Oligomaleinsäuren, Copolymere der Maleinsäure mit Acrylsäure, Methacrylsäure oder C2-C22-Olefinen, z.B. Isobuten oder langkettigen α-Olefinen, mit Vinyl-C1-C8-alkylether, Vinylacetat, Vinylpropionat, (Meth)acrylsäureester von C1-C8-Alkoholen und/oder Styrol, Copolymere der Acrylsäure mit Methacrylsäure oder C2-C22-Olefinen, z.B. Isobuten oder langkettigen α-Olefinen, insbesondere mit C10-C22-α-Olefinen, Vinyl-C1-C8-alkylether, Vinylacetat, Vinylpropionat, (Meth)acrylsäureester von C1-C8-Alkoholen und Styrol. Bevorzugt sind die Homopolymere der Acrylsäure und Copolymere von Acrylsäure mit Maleinsäure. Oligomeren und polymeren Carbonsäuren werden in Säureform oder als Natriumsalz eingesetzt.
- Low molecular weight Cärbonsäuren such as citric acid, hydrophobically modified citric acid, z. B. agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl and Alkenylsuccinic acids and aminopolycarboxylic acids, eg nitrilotriacetic acid, .beta.-alanine-diacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, ethylenediamine disuccinic acid and methyl- and ethylglycinediacetic acid.
- Oligomeric and polymeric carboxylic acids, such as homopolymers of acrylic acid and aspartic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid or C 2 -C 22 -olefins, for example isobutene or long-chain α-olefins, with vinyl-C 1 -C 8 -alkyl ether, vinyl acetate , Vinyl propionate, (meth) acrylic esters of C 1 -C 8 -alcohols and / or styrene, copolymers of acrylic acid with methacrylic acid or C 2 -C 22 -olefins, for example isobutene or long-chain α-olefins, in particular with C 10 -C 22 - α-olefins, vinyl-C 1 -C 8 -alkyl ethers, vinyl acetate, vinyl propionate, (meth) acrylic acid esters of C 1 -C 8 -alcohols and styrene. Preferred are the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. Oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.
Geeignete Bleichmittel sind beispielsweise Addukte von Wasserstoffperoxid an anorganische Salze, wie Natriumperborat-Monohydrat, Natriumperborat-Tetrahydrat und Natriumcarbonat-Perhydrat, und Percarbonsäuren, wie Phthalimidopercapronsäure.Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.
Als Bleichaktivatoren eignen sich z.B. N,N,N',N'-Tetraacetylethylendiamin (TAED), Natrium-p-nonanoyloxybenzolsulfonat und N-Methylmorpholiniumacetonitrilmethyl-sulfat.Suitable bleach activators are e.g. N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methyl sulfate.
Vorzugsweise in Waschmitteln eingesetzte Enzyme sind Proteasen, Lipasen, Amylasen, Cellulasen, Oxidasen und Peroxidasen.Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.
Geeignete Farbübertragungsinhibitoren sind beispielsweise Homo-, Co- und Pfropfpolymere von 1-Vinylpyrrolidon, 1-Vinylimidazol oder 4-Vinylpyridin-N-oxid. Auch mit Chloressigsäure umgesetzte Homo- und Copolymere des 4-Vinylpyridins eignen sich als Farbübertragungsinhibitoren.Suitable color transfer inhibitors are, for example, homo-, co- and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine-N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.
Weitere an sich übliche Waschmittelinhaltsstoffe sind bekannt. Detaillierte Beschreibungen sind z. B. in
Es wurde außerdem gefunden, dass man erfindungsgemäße Copolymerisate und wässrige Dispersionen oder Lösungen von erfindungsgemäßem Copolymerisat als Verdicker in Reinigern für harte Oberflächen verwenden kann. Gegenstand der vorliegenden Erfindung ist daher die Verwendung von erfindungsgemäßen Copolymerisaten und von wässrigen Dispersionen oder Lösungen von erfindungsgemäßem Copolymerisat als Zusatzmittel für Reiniger für harte Oberflächen. Ein weiterer Gegenstand der vorliegenden Erfindung sind Reiniger für harte Oberflächen, enthaltend erfindungsgemäßes Copolymerisat. Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Reinigung von harten Oberflächen unter Verwendung von erfindungsgemäßem Copolymerisat oder von wässrigen Dispersionen oder Lösungen von erfindungsgemäßem Copolymerisat.It has also been found that copolymers according to the invention and aqueous dispersions or solutions of copolymer according to the invention can be used as thickeners in hard surface cleaners. The present invention therefore relates to the use of copolymers according to the invention and of aqueous dispersions or solutions of copolymer according to the invention as additives for hard surface cleaners. Another object of the The present invention relates to hard surface cleaners containing the copolymer of the invention. Another object of the present invention is a process for the purification of hard surfaces using copolymer of the invention or aqueous dispersions or solutions of copolymer of the invention.
Unter Reinigern für harte Oberflächen sollen beispielsweise Reiniger für die Metall-, Kunststoff-, Glas- und Keramikreinigung, Fußbodenreiniger, Sanitärreiniger, Allzweckreiniger im Haushalt und in gewerblichen Anwendungen, technische Reiniger (für den Einsatz in Autowaschanlagen oder Hochdruckreinigern), Kaltreiniger, Geschirreiniger, Klarspüler, Desinfektionsreiniger, Reiniger für die Nahrungsmittel- und Getränkeindustrie, insbesondere als Flaschenreiniger, als CIP-Reiniger (Cleaning-in-Place) in Molkereien, Brauereien und sonstigen Betrieben von Nahrungsmittelherstellern verstanden werden. Reiniger, welche erfindungsgemäßes Copolymerisat enthalten, eignen sich besonders zum Reinigen harter Oberflächen wie Glas, Kunststoff und Metall. Die Reiniger können alkalisch, sauer oder neutral eingestellt sein. Sie enthalten üblicherweise ein oder mehrere Tenside in Mengen von etwa 0,2 bis 50 Gew.-%. Dabei kann es sich um anionische, nicht-ionische oder kationische Tenside sowie um Mischungen von Tensiden handeln, die miteinander verträglich sind, z.B. Mischungen aus anionischen und nicht-ionischen oder aus kationischen und nicht-ionischen Tensiden. Alkalische Reiniger können enthalten Soda, Pottasche, Natriumhydrogencarbonat, Kaliumhydrogencarbonat, Natriumsesquicarbonat, Kaliumsesquicarbonat, Natriumhydroxid, Kaliumhydroxid, Aminbasen wie Monoethanolamin, Diethanolamin, Triethanolamin, Ammoniak oder Silikat in Mengen bis zu 60 Gew.-%, in einigen Fällen sogar bis zu 80 Gew.-%. Erfindungsgemäße Reiniger für harte Oberflächen können außerdem Zitrate, Glukonate oder Tartrate in Mengen bis zu 80 Gew.-% enthalten. Erfindungsgemäße Reiniger für harte Oberflächen können in fester oder in flüssiger Form vorliegen.Cleaners for hard surfaces include, for example, cleaners for metal, plastic, glass and ceramic cleaning, floor cleaners, sanitary cleaners, all-purpose household and commercial cleaners, technical cleaners (for use in car washes or high-pressure cleaners), cold cleaners, dishwashing detergents, rinse aids , Disinfectant cleaners, cleaners for the food and beverage industry, especially as bottle cleaners, as CIP cleaners (cleaning-in-place) in dairies, breweries and other establishments understood by food manufacturers. Cleaners containing copolymer of the invention are particularly suitable for cleaning hard surfaces such as glass, plastic and metal. The cleaners can be alkaline, acidic or neutral. They usually contain one or more surfactants in amounts of about 0.2 to 50 wt .-%. These may be anionic, nonionic or cationic surfactants, as well as mixtures of surfactants which are compatible with each other, e.g. Mixtures of anionic and nonionic or of cationic and nonionic surfactants. Alkaline cleaners may include soda, potash, sodium bicarbonate, potassium bicarbonate, sodium sesquicarbonate, potassium sesquicarbonate, sodium hydroxide, potassium hydroxide, amine bases such as monoethanolamine, diethanolamine, triethanolamine, ammonia or silicate in amounts up to 60% by weight, in some cases even up to 80%. -%. Hard surface cleaners according to the invention may also contain citrates, gluconates or tartrates in amounts of up to 80% by weight. Hard surface cleaners of the present invention may be in solid or liquid form.
In einer Ausführungsform der vorliegenden Erfindung ist erfindungsgemäßes Copolymerisat in erfindungsgemäßen Reinigern für harte Oberflächen in Mengen von 0,1 bis 20, vorzugsweise 0,2 bis 15 Gew.-% enthalten.In one embodiment of the present invention, copolymer of the invention is contained in hard surface cleaners according to the invention in amounts of from 0.1 to 20, preferably from 0.2 to 15,% by weight.
Ein weiterer Gegenstand der vorliegenden Erfindung sind kosmetische Zubereitungen, enthaltend mindestens ein erfindungsgemäßes Copolymer. Erfindungsgemäße kosmetische Zubereitungen können beispielsweise zur Pflege von Haut, Haar, Hornhaut, Finger- oder Fußnägeln oder zur Mundpflege eingesetzt werden.Another object of the present invention are cosmetic preparations containing at least one inventive copolymer. Cosmetic preparations according to the invention can be used, for example, for the care of skin, hair, cornea, fingernails or toenails or for oral care.
Erfindungsgemäße kosmetische Zubereitungen können als wässrige oder wässrigalkoholische Lösungen, als O/W- oder W/O-Emulsionen vorliegen.Cosmetic preparations according to the invention can be present as aqueous or aqueous-alcoholic solutions, as O / W or W / O emulsions.
In einer Ausführungsform der vorliegenden Erfindung liegen erfindungsgemäße kosmetische Zubereitungen in Form von Shampoos, Cremes, Schäumen, Sprays (Pumpspray oder Aerosol), Gelen, Gelsprays, Lotionen oder Mousse liegen und können dementsprechend mit üblichen weiteren Hilfsstoffen formuliert werden.In one embodiment of the present invention, cosmetic preparations according to the invention are in the form of shampoos, creams, foams, sprays (pump spray or aerosol), gels, gel sprays, lotions or mousses and can accordingly be formulated with conventional further auxiliaries.
Bei den erfindungsgemäßen kosmetischen Zubereitungen kann es sich um hautkosmetische, haarkosmetische, pharmazeutische, hygienische oder pharmazeutische Mittel handeln. Aufgrund ihrer filmbildenden Eigenschaften eignen sich die zuvor beschriebenen Copolymere insbesondere als Zusatzstoffe für Haar- und Hautkosmetika.The cosmetic preparations according to the invention may be skin-cosmetic, hair-cosmetic, pharmaceutical, hygienic or pharmaceutical agents. Due to their film-forming properties, the copolymers described above are particularly suitable as additives for hair and skin cosmetics.
Vorzugsweise liegen erfindungsgemäße kosmetische Zubereitungen in Form eines Sprays, eines Gels, eines Schaums, einer Salbe, Creme, einer Emulsion, einer Süspension, einer Lotion, einer Milch oder einer Paste vor. Gewünschtenfalls können auch Liposomen oder Mikrosphären eingesetzt werden.Cosmetic preparations according to the invention are preferably in the form of a spray, a gel, a foam, an ointment, cream, an emulsion, a suspension, a lotion, a milk or a paste. If desired, liposomes or microspheres can also be used.
Neben erfindungsgemäßem Copolymer können erfindungsgemäße kosmetische Zubereitungen mindestens einen Träger enthalten. Beispiele für geeignete Träger sind:
- i) Wasser,
- ii) wassermischbare organische Lösungsmittel, vorzugsweise C2-C4-Alkanolen, insbesondere Ethanol,
- iii) Öle, Fette, Wachse,
- iv) von iii) verschiedenen Ester von C6-C30-Monocarbonsäuren mit ein-, zwei- oder dreiwertigen Alkoholen,
- v) gesättigte acyclische und cyclische Kohlenwasserstoffen,
- vi) Fettsäuren,
- vii) Fettalkohole,
- viii) Treibgase,
- i) water,
- ii) water-miscible organic solvents, preferably C 2 -C 4 -alkanols, in particular ethanol,
- iii) oils, fats, waxes,
- iv) different esters of C 6 -C 30 monocarboxylic acids with monohydric, dihydric or trihydric alcohols,
- v) saturated acyclic and cyclic hydrocarbons,
- vi) fatty acids,
- vii) fatty alcohols,
- viii) propellants,
Beispiele für Träger sind insbesondere Öle und Fette, gewählt aus Kohlenwasserstoffen geringer Polarität, wie Mineralölen; linearen gesättigten Kohlenwasserstoffen, vorzugsweise mit mehr als 8 C-Atomen wie Tetradecan, Hexadecan, Octadecan etc., cyclischen Kohlenwasserstoffen wie Decahydronaphthalin, verzweigten Kohlenwasserstoffen; tierischen und pflanzlichen Ölen, Wachsen, Wachsestern, Vaselin, Estern, bevorzugt Estern von Fettsäuren, wie z. B. die Ester von C1-C40-Monoalkanolen mit C1-C22-Monocarbonsäuren, wie Isopropylisostearat, n-Propylmyristat, iso-Propylmyristat, n-Propylpalmitat, iso-Propylpalmitat, Hexacosanylpalmitat, Octacosanylpalmitat, Triacontanylpalmitat, Dotriacontanylpalmitat, Tetratriacontanylpalmitat, Hexancosanylstearat, Octacosanylstearat, Triacontanylstearat, Dotriacontanylstearat, Tetratriacontanylstearat, Salicylaten, wie C1-C10-Salicylaten, z. B. Octylsalicylat, Benzoatestern wie C10-C15-Alkylbenzoaten, Benzylbenzoat, anderen kosmetischen Estern, wie Fettsäuretriglyceriden, Propylenglykolmonolaurat, Polyethylenglykolmonolaurat, C10-C15-Alkyllactaten und Mischungen davon.Examples of carriers are, in particular, oils and fats selected from low polarity hydrocarbons, such as mineral oils; linear saturated hydrocarbons, preferably having more than 8 carbon atoms, such as tetradecane, hexadecane, octadecane, etc., cyclic hydrocarbons, such as decahydronaphthalene, branched hydrocarbons; animal and vegetable oils, waxes, wax esters, petrolatum, esters, preferably esters of fatty acids, such as. The esters of C 1 -C 40 monoalkanols with C 1 -C 22 monocarboxylic acids such as isopropyl isostearate, n-propyl myristate, isopropyl myristate, n-propyl palmitate, iso-propyl palmitate, hexacosanyl palmitate, octacosanyl palmitate, triacontanyl palmitate, dotriacontanyl palmitate, tetratriacontanyl palmitate, Hexancosanyl stearate, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriacontanyl stearate, salicylates such as C 1 -C 10 salicylates, e.g. Octyl salicylate, benzoate esters such as C 10 -C 15 alkyl benzoates, benzyl benzoate, other cosmetic esters such as fatty acid triglycerides, Propylene glycol monolaurate, polyethylene glycol monolaurate, C 10 -C 15 alkyl lactates and mixtures thereof.
Als Träger geeignete Siliconöle sind z. B. lineare Polydimethylsiloxane, Poly(methylphenylsiloxane), cyclische Siloxane und Mischungen davon. Das zahlenmittlere Molekulargewicht der Polydimethylsiloxane und Poly(methylphenylsiloxane) liegt vorzugsweise in einem Bereich von etwa 1000 bis 150000 g/mol. Bevorzugte cyclische Siloxane weisen 4- bis 8-gliedrige Ringe auf. Geeignete cyclische Siloxane sind z. B. unter der Bezeichnung Cyclomethicon kommerziell erhältlich.As carrier suitable silicone oils are z. As linear polydimethylsiloxanes, poly (methylphenylsiloxanes), cyclic siloxanes and mixtures thereof. The number average molecular weight of the polydimethylsiloxanes and poly (methylphenylsiloxanes) is preferably in a range of about 1,000 to 150,000 g / mol. Preferred cyclic siloxanes have 4- to 8-membered rings. Suitable cyclic siloxanes are, for. B. under the name cyclomethicone commercially available.
Als Träger bevorzugte Öl- bzw. Fettkomponenten sind ausgewählt unter Paraffin und Paraffinölen, Vaselin, natürlichen Fetten und Ölen wie Castoröl, Sojaöl, Erdnussöl, Olivenöl, Sonnenblumenöl, Sesamöl, Avocadoöl, Kakaobutter, Mandelöl, Pfirsichkernöl, Ricinus-öl, Lebertran, Schweineschmalz, Walrat, Spermacetöl, Spermöl, Weizenkeimöl, Macadamianussöl, Nachtkerzenöl, Jojobaöl, Fettalkoholen, wie Laurylälkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Oleylalkohol, Cetylalkohol, Fettsäuren, wie Myristinsäure, Stearinsäure, Palmitinsäure, Ölsäure, Linolsäure, Linolensäure und davon verschiedenen gesättigten, ungesättigten und substituierten Fettsäuren; Wachsen, wie Bienenwachs, Carnaubawachs, Candilillawachs, Walrat sowie Mischungen der zuvor genannten Öl- bzw. Fettkomponenten.Carrier preferred oil or fat components are selected from paraffin and paraffin oils, vaseline, natural fats and oils such as castor oil, soybean oil, peanut oil, olive oil, sunflower oil, sesame oil, avocado oil, cocoa butter, almond oil, peach kernel oil, castor oil, cod liver oil, lard, Spermacetöl, sperm oil, wheat germ oil, Macadamianussöl, evening primrose oil, jojoba oil, fatty alcohols such as lauryl, myristyl, cetyl, stearyl, oleyl, cetyl, fatty acids such as myristic, stearic, palmitic, oleic, linoleic, and various saturated, unsaturated and substituted fatty acids; Waxes, such as beeswax, carnauba wax, candililla wax, spermaceti and mixtures of the aforementioned oil or fat components.
Neben erfindungsgemäßem Copolymer und Träger können erfindungsgemäße kosmetische Zubereitungen enthalten: wenigstens einen von Träger und erfindungsgemäßem Copolymer verschiedenen Bestandteil, der ausgewählt ist unter kosmetisch wirksamen Pflege- und Wirkstoffen wie AHA-Säuren, Fruchtsäuren, Ceramiden, Phytantriol, Collagen, Vitaminen und Provitaminen, beispielsweise Vitamin A, E und C, Retinol, Bisabolol, Parithenol, Emulgatoren und Co-Emulgatoren, Tensiden, Konservierungsmitteln, Parfümölen, Haarpolymeren, Haar- und Hautconditionern, Pfropfpolymeren, Silikonverbindungen, wasserlöslichen oder dispergierbaren silikonhaltigen Polymeren, natürlichen und synthetischen Lichtschutzmitteln, Bleichmitteln, Gelbildnern, Pflegemitteln, Färbemitteln, Farbstoffen, Pigmenten, Mikropigmente wie Titanoxid oder Zinkoxid, Trübungsmitteln, Tönungsmitteln, Bräunungsmitteln, Konsistenzgebern, Feuchthaltemitteln, Rückfettern, Collagen, Eiweißhydrolysaten, Lipiden, Antioxidantien, Entschäumern, Antistatika, Emollienzien, Lösungsvermittlern, Repellents, Überfettungsmitteln, Perlglanzwachsen, Konsistenzgebern, Solubilisatoren, Komplexbildnern, pH-Wert Regulatoren, Reflektoren, Proteinen und Proteinhydrolysaten (z.B. Weizen-, Mandel- oder Erbsenproteine) und Weichmachern.In addition to the copolymer and carrier according to the invention, cosmetic preparations according to the invention may comprise at least one component which is different from the carrier and inventive copolymer and is selected from cosmetically active care agents and active ingredients such as AHA acids, fruit acids, ceramides, phytantriol, collagen, vitamins and provitamins, for example vitamin A, E and C, retinol, bisabolol, parithenol, emulsifiers and co-emulsifiers, surfactants, preservatives, perfume oils, hair polymers, hair and skin conditioners, graft polymers, silicone compounds, water-soluble or dispersible silicone-containing polymers, natural and synthetic sunscreens, bleaches, gelling agents, Care products, colorants, dyes, pigments, micropigments such as titanium oxide or zinc oxide, opacifiers, tinting agents, tanning agents, bodying agents, moisturizers, re-fats, collagen, protein hydrolysates, lipids, antioxidants, Ent foaming agents, antistatics, emollients, solubilizers, repellents, superfatting agents, pearlescent waxes, bodying agents, solubilizers, complexing agents, pH regulators, reflectors, proteins and protein hydrolysates (e.g. Wheat, almond or pea proteins) and plasticizers.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Verbindungen (B). Erfindungsgemäße Verbindungen (B) weisen pro Molekül mindestens eine Struktureinheit der allgemeinen Formel I auf,
Dabei sind die Variablen wie vorstehend definiert:
- R1
- verschieden oder vorzugsweise gleich und gewählt aus Wasserstoff oder bevorzugt C6-C30-Aryl, bevorzugt C6-C14-Aryl, insbesondere Phenyl; C7-C30-Aralkyl, bevorzugt Benzyl; C3-C10-Cycloalkyl, insbesondere Cyclopentyl oder Cyclohexyl, und insbesondere C1-C30-Alkyl, bevorzugt C1-C20-Alkyl.
- A1
- verschieden oder vorzugsweise gleich und gewählt aus C6-C10-Arylen, vorzugsweise Phenylen, C7-C10-Aralkylen wie beispielsweise -CH(C6H5)- oder -CH2-CH(C6H5)-, und insbesondere aus C2-C10-Alkylen, substituiert oder vorzugsweise nicht substituiert, bevorzugt -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, ganz besonders bevorzugt -CH2-CH2-,
- n
- verschieden oder gleich und gewählt aus null bis 200, bevorzugt 1 bis 150, besonders bevorzugt 5 bis 50,
- m
- gewählt aus 1 bis 6, bevorzugt bis 4, besonders bevorzugt bis 2.
- R 1
- different or preferably identical and selected from hydrogen or preferably C 6 -C 30 -aryl, preferably C 6 -C 14 -aryl, in particular phenyl; C 7 -C 30 aralkyl, preferably benzyl; C 3 -C 10 -cycloalkyl, in particular cyclopentyl or cyclohexyl, and in particular C 1 -C 30 -alkyl, preferably C 1 -C 20 -alkyl.
- A 1
- different or preferably identical and selected from C 6 -C 10 -aryls, preferably phenylene, C 7 -C 10 -aralkylenes such as -CH (C 6 H 5 ) - or -CH 2 -CH (C 6 H 5 ) -, and in particular from C 2 -C 10 -alkylene, substituted or preferably unsubstituted, preferably -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 3 ) -, very particularly preferably -CH 2 -CH 2 -,
- n
- different or the same and selected from zero to 200, preferably from 1 to 150, particularly preferably from 5 to 50,
- m
- selected from 1 to 6, preferably to 4, more preferably to 2.
In einer Ausführungsform der vorliegenden Erfindung weist erfindungsgemäße Verbindung (B) ein Molekulargewicht Mw im Bereich von 200 bis 100.000 g/mol auf, bevorzugt bis 10.000 g/mol, besonders bevorzugt bis 5.000 g/mol, bestimmt beispielsweise durch Gelpermeationschromatograhie (GPC). Ein geeigneter Standard ist beispielsweise Polymethylmethacrylat (PMMA).In one embodiment of the present invention, compound (B) according to the invention has a molecular weight M w in the range from 200 to 100,000 g / mol, preferably up to 10,000 g / mol, particularly preferably up to 5,000 g / mol, determined for example by gel permeation chromatography (GPC). A suitable standard is, for example, polymethyl methacrylate (PMMA).
In einer Ausführungsform der vorliegenden Erfindung weist Verbindung (B) einen K-Wert nach Fikentscher im Bereich von 8 bis 40 auf, gemessen bei 23°C in THF/Wasser-Gemischen, vorzugsweise in 2 Gew.-% Lösung in THF.In one embodiment of the present invention, compound (B) has a Fikentscher K value in the range of 8 to 40, measured at 23 ° C. in THF / water mixtures, preferably in 2% by weight solution in THF.
In einer Ausführungsform der vorliegenden Erfindung weist erfindungsgemäßes Verbindung (B) eine Polydispersität Mn/Mw im Bereich von 1 bis 4 auf, bevorzugt von 1,1 bis 2 und besonders bevorzugt im Bereich von 1,1 bis 1,5.In one embodiment of the present invention, compound (B) according to the invention has a polydispersity M n / M w in the range from 1 to 4, preferably from 1.1 to 2 and particularly preferably in the range from 1.1 to 1.5.
In einer Ausführungsform der vorliegenden Erfindung ist mindestens eine Struktureinheit der allgemeinen Formel I über eine Gruppe der Formel III a
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäße Verbindung (B) mindestens ein Comonomer der allgemeinen Formel IV a oder IV b einpolymerisiert,
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von erfindungsgemäßen Verbindungen (B), das dadurch gekennzeichnet ist, dass man mindestens ein (Co)monomer der allgemeinen Formel IV a oder IV b
- R2, R3
- gleich oder verschieden und gewählt aus C1-C6-Alkyl, bevorzugt n-C1-C4-Alkyl, besonders bevorzugt Methyl und insbesondere Wasserstoff,
- R4
- C1-C6-Alkyl, bevorzugt n-C1-C4-Alkyl, besonders bevorzugt Methyl, bevorzugt COOM und insbesondere Wasserstoff,
- M
- gewählt aus Ammonium, substituiert oder vorzugsweise unsubstituiert, Wasserstoff und Metallkationen, insbesondere Alkalimetallkationen oder einem halben Äquivalent Erdalkalimetallkationen,
- R5
- gewählt aus Wasserstoff und Methyl,
- t
- gewählt aus null und eins.
- w
- gewählt aus null und eins,
- A2
- wird gewählt aus C1-C50-Alkylen, substituiert oder vorzugsweise nicht substituiert, wobei eine oder mehrere nicht-benachbarte CH2-Gruppen durch Sauerstoff ersetzt sein können. Beispiele für geeignete Gruppen A2 sind C2-C10-Alkylen, bevorzugt -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, besonders bevorzugt -CH2-CH2-, weiterhin -CH2-CH2-O-, -CH(CH3)-CH2-O-, -CH2-CH(CH3)-O-, -[CH2-CH2-O]y-, -[CH(CH3)-CH2-O]y-, -[CH2-CH(CH3)-O-]y, wobei y eine ganze Zahl im Bereich von 2 bis 20, bevorzugt 2 bis 15 und insbesondere 3 bis 10 ist.
- R 2 , R 3
- identical or different and selected from C 1 -C 6 -alkyl, preferably nC 1 -C 4 -alkyl, particularly preferably methyl and in particular hydrogen,
- R 4
- C 1 -C 6 -alkyl, preferably nC 1 -C 4 -alkyl, particularly preferably methyl, preferably COOM and in particular hydrogen,
- M
- selected from ammonium, substituted or preferably unsubstituted, hydrogen and metal cations, in particular alkali metal cations or half an equivalent of alkaline earth metal cations,
- R 5
- selected from hydrogen and methyl,
- t
- chosen from zero and one.
- w
- chosen from zero and one,
- A 2
- is selected from C 1 -C 50 alkylene, substituted or preferably unsubstituted, wherein one or more non-adjacent CH 2 groups may be replaced by oxygen. Examples of suitable groups A 2 are C 2 -C 10 -alkylene, preferably -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 3 ) -, more preferably -CH 2 -CH 2 -, furthermore -CH 2 -CH 2 -O-, -CH (CH 3 ) -CH 2 -O-, -CH 2 -CH (CH 3 ) -O-, - [CH 2 -CH 2 -O] y -, - [CH (CH 3 ) -CH 2 -O] y -, - [CH 2 -CH (CH 3 ) -O-] y , where y is an integer in the range from 2 to 20, preferably 2 to 15 and in particular 3 to 10.
Beispielsweise kann man erfindungsgemäße Verbindungen (B) wie folgt herstellern.For example, compounds (B) according to the invention can be prepared as follows.
Man stellt zunächst eine Verbindung der allgemeinen Formel VI a her,
Die Herstellung von Verbindung der allgemeinen Formel VI bzw. VI a kann man in Gegenwart eines Katalysators durchführen. Geeignete Katalysatoren sind beispielsweise anorganische und organische Basen. Setzt man Epichlorhydrin als reaktives Glycerinderivat ein, so dient Base nicht nur als Katalysator, sondern auch zum Neutralisieren der entstehenden HCl. Geeignete anorganische Basen sind beispielsweise Alkalimetallcarbonate und insbesondere Alkalimetallhydroxide wie NaOH und KOH. Geeignete organische Basen sind beispielsweise tertiäre Amine, insbesondere Triethylamin und [2,2,2]Diazabicyclooctan (DABCO), sowie Pyridin und para-N,N-Dimethylaminopyridin.The preparation of compound of general formula VI or VI a can be carried out in the presence of a catalyst. Suitable catalysts are, for example, inorganic and organic bases. When epichlorohydrin is used as the reactive glycerol derivative, the base serves not only as a catalyst but also to neutralize the resulting HCl. Suitable inorganic bases are, for example, alkali metal carbonates and in particular alkali metal hydroxides such as NaOH and KOH. Suitable organic bases are, for example, tertiary amines, in particular triethylamine and [2,2,2] diazabicyclooctane (DABCO), and also pyridine and para-N, N-dimethylaminopyridine.
In einer Ausführungsform der vorliegenden Erfindung kann man die Herstellung von Verbindung der allgemeinen Formel VI bzw. VIa in einem Lösungsmittel durchführen. Geeignete Lösungsmittel sind beispielsweise Ether, insbesondere 1,4-Dioxan, Diisopropylether, Tetrahydrofuran ("THF") und Di-n-butylether. Weitere geeignete Lösungsmittel sind n-Butylacetat ("Butylacetat"), DMSO, N,N-Dimethylformamid ("DMF") und N-Methylpyrrolidon und aromatische Lösungsmittel wie beispielsweise Toluol.In one embodiment of the present invention, it is possible to carry out the preparation of compound of the general formula VI or VIa in a solvent. Suitable solvents are, for example, ethers, in particular 1,4-dioxane, diisopropyl ether, tetrahydrofuran ("THF") and di-n-butyl ether. Further suitable solvents are n-butyl acetate ("butyl acetate"), DMSO, N, N-dimethylformamide ("DMF") and N-methylpyrrolidone and aromatic solvents such as toluene.
In Ausführungsformen, in denen bei der Herstellung von Verbindung der allgemeinen Formel VI Wasser abgespalten wird, kann man Wasser entziehendes Mittel einsetzen, beispielsweise Molekularsieb, Natriumsulfat, Magnesiumsulfat, oder man kann das gebildete Wasser durch azeotrope Destillation entfernen.In embodiments in which water is split off in the preparation of compound of the general formula VI, it is possible to use a dehydrating agent, for example molecular sieve, sodium sulfate, magnesium sulfate, or the water formed can be removed by azeotropic distillation.
In einer Ausführungsform der vorliegenden Erfindung führt man die Umsetzung zu Verbindung der allgemeinen Formel VI über einen Zeitraum von 15 Minuten bis 48 Stunden durch, bevorzugt 1 bis 24 Stunden, besonderes bevorzugt 3 bis 15 Stunden.In one embodiment of the present invention, the reaction is carried out to give compounds of general formula VI over a period of 15 minutes to 48 hours, preferably 1 to 24 hours, more preferably 3 to 15 hours.
In einer Ausführungsform der vorliegenden Erfindung führt man die Umsetzung zu Verbindung der allgemeinen Formel VI stufenweise durch, und zwar in so vielen Stufen, wie sie dem gewünschten m entspricht. Dabei wird reaktives Derivat von Glycerin, insbesondere Epichlorhydrin in der betreffenden Zahl an Stufen zugesetzt. Zur stufeweisen Umsetzung kann man beispielsweise so vorgehen, dass man zunächst eine bestimmte Menge an Verbindung der allgemeinen Formel R1-(O-A1)n-OH mit der halben Molzahl an Glycerin oder vorzugsweise mit einem reaktiven Derivat von Glycerin, insbesondere mit Epichlorhydrin, umsetzt. Danach gibt man eine Menge an Glycerin oder an reaktivem Derivat von Glycerin zu, die einem Viertel der Molzahl von Verbindung der allgemeinen Formel R1-(O-A1)n-OH entspricht, und setzt um. Wünscht man eine weitere Stufe durchzuführen, so gibt man danach eine Menge an Glycerin oder an reaktivem Derivat von Glycerin zu, die einem Achtel der Molzahl an Verbindung der allgemeinen Formel R1-(O-A1)n-OH entspricht, und setzt um. Bei jeder weiteren Stufe reduziert man die zugesetzte Molzahl an Verbindung der allgemeinen Formel R1-(O-A1)n-OH entsprechend.In one embodiment of the present invention, the reaction to give the compound of general formula VI is carried out stepwise, in as many stages as it corresponds to the desired m. In this case, reactive derivative of glycerol, in particular epichlorohydrin in the number of stages is added. For example, the stepwise reaction can be carried out by first reacting a certain amount of compound of the general formula R 1 - (OA 1 ) n -OH with half the number of moles of glycerol or preferably with a reactive derivative of glycerol, in particular with epichlorohydrin , Thereafter, an amount of glycerol or reactive derivative of glycerol is added, which corresponds to a quarter of the number of moles of compound of the general formula R 1 - (OA 1 ) n -OH, and converts. If it is desired to carry out a further step, then an amount of glycerol or reactive derivative of glycerol corresponding to one-eighth the number of moles of compound of general formula R 1 - (OA 1 ) n -OH is added and reacted. In each further step, the added number of moles of compound of the general formula R 1 - (OA 1 ) n -OH is reduced accordingly.
In einem weiteren Schritt kann man Verbindung der allgemeinen Formel VI mit einer Verbindung mit einer ethylenischen Doppelbindung umsetzen.In a further step, compound of the general formula VI can be reacted with a compound having an ethylenic double bond.
Beispielsweise kann man Verbindung der allgemeinen Formel VI mit einem hinreichend reaktiven Derivat einer ethylenisch ungesättigten Carbonsäure oder einer ethylenisch ungesättigten Dicarbonsäure, beispielsweise mit Säurechlorid oder Säureanhydrid, insbesondere mit (Meth)acrylsäureanhydrid umsetzen und erhält erfindungsgemäße Verbindung der Formel IV a, in der t = 1 ist und die übrigen Variablen wie vorstehend definiert sind.
In einer Ausführungsform der vorliegenden Erfindung führt man die Umsetzung von Verbindung der allgemeinen Formel VI zu Verbindung der allgemeinen Formel IV bei Temperaturen im Bereich von - 20 bis +70 °C, bevorzugt von +15 bis 50 °C durch.In one embodiment of the present invention, the reaction of compound of the general formula VI to give the compound of the general formula IV is carried out at temperatures in the range from -20 to + 70 ° C., preferably from +15 to 50 ° C.
In einer Ausführungsform der vorliegenden Erfindung führt man die Umsetzung von Verbindung der allgemeinen Formel VI zu Verbindung der allgemeinen Formel IV in einem Lösungsmittel oder einem Gemisch von Lösungsmitteln durch. Geeignete Lösungsmittel sind beispielsweise Ether, insbesondere Tetrahydrofuran, Diethylether, 1,4-Dioxan, Aceton, oder apolare Lösungsmittel wie beispielsweise N,N-Dimethylformamid ("DMF"), Dimethylsulfoxid (DMSO) oder Kohlenwasserstoffe, beispielsweise Cyclohexan.In one embodiment of the present invention, the reaction of compound of the general formula VI to give the compound of the general formula IV in a solvent or a mixture of solvents. Suitable solvents are, for example, ethers, in particular tetrahydrofuran, diethyl ether, 1,4-dioxane, acetone, or apolar solvents such as, for example, N, N-dimethylformamide ("DMF"), dimethylsulfoxide (DMSO) or hydrocarbons, for example cyclohexane.
In einer Ausführungsform der vorliegenden Erfindung führt man die Umsetzung von Verbindung der allgemeinen Formel VI zu Verbindung der allgemeinen Formel IV in Gegenwart von Katalysator durch. Geeignete Katalysatoren sind beispielsweise Basen, beispielsweise Natriumhydrid und insbesondere tertiäre Amine wie beispielsweise N,N-Dimethylaminopyridin. Katalysatoren werden im Allgemeinen in unterstöchiometrischen Mengen eingesetzt. Wünscht man jedoch, die als reaktives Säurederivat ein Säurehalogenid einzusetzen, so kann man mit einem Überschuss an Base arbeiten, wobei die Base gleichzeitig die gebildete Säure neutralisiert und als Katalysator dienen kann.In one embodiment of the present invention, the reaction of compound of general formula VI to give compound of general formula IV in the presence of catalyst. Suitable catalysts are for example bases, for example sodium hydride and in particular tertiary amines such as N, N-dimethylaminopyridine. Catalysts are generally used in substoichiometric amounts. However, if it is desired to use an acid halide as the reactive acid derivative, it is possible to work with an excess of base, whereby the base can simultaneously neutralize the acid formed and serve as a catalyst.
In einer Ausführungsform der vorliegenden Erfindung führt man die Umsetzung von Verbindung der allgemeinen Formel VI zu Verbindung der allgemeinen Formel IV über einen Zeitraum von 15 Minuten bis 12 Stunden durch, bevorzugt sind 1 bis 5 Stunden.In one embodiment of the present invention, the reaction of compound of the general formula VI to give the compound of the general formula IV is carried out over a period of 15 minutes to 12 hours, preference being given to 1 to 5 hours.
In einer anderen Ausführungsform der vorliegenden Erfindung kann man Verbindung der allgemeinen Formel VI mit Acetylen umsetzen und erhält erfindungsgemäße Verbindung der Formel IV a, in der t = null ist und die übrigen Variablen wie vorstehend definiert sind.In another embodiment of the present invention, one can react compound of the general formula VI with acetylene and obtains the compound according to the invention of formula IV a, where t = zero and the remaining variables are as defined above.
Zur Umsetzung mit Acetylen kann man einen oder mehrere Katalysatoren, bevorzugt gewählt aus basischen Katalysatoren einsetzen. Besonders geeignet ist KOH.For the reaction with acetylene, it is possible to use one or more catalysts, preferably selected from basic catalysts. Especially suitable is KOH.
Die Umsetzung mit Acetylen kann man mit oder ohne Lösungsmittel durchführen. Geeignete Lösungsmittel sind beispielsweise N-Methylpyrrolidon, N-Ethylpyrrolidon, Toluol, Xylol, THF und Dioxan.The reaction with acetylene can be carried out with or without solvent. Suitable solvents are, for example, N-methylpyrrolidone, N-ethylpyrrolidone, toluene, xylene, THF and dioxane.
Die Umsetzung mit Acetylen kann man beispielsweise bei Temperaturen im Bereich von 80 bis 160°C durchführen, bevorzugt sind Temperaturen um 120°C, beispielsweise 110 bis 130°C.The reaction with acetylene can be carried out, for example, at temperatures in the range from 80 to 160.degree. C., temperatures of around 120.degree. C., for example 110 to 130.degree. C., are preferred.
Die Umsetzung mit Acetylen kann man bei Normaldruck durchführen oder vorzugsweise bei erhöhtem Druck, beispielsweise bei 2 bis 30 bar.The reaction with acetylene can be carried out at atmospheric pressure or preferably at elevated pressure, for example at 2 to 30 bar.
In einer Ausführungsform der vorliegenden Erfindung führt man die Umsetzung mit Acetylen über einen Zeitraum von 15 Minuten bis 48 Stunden durch, bevorzugt bis 36 Stunden.In one embodiment of the present invention, the reaction with acetylene is carried out over a period of 15 minutes to 48 hours, preferably up to 36 hours.
In einer anderen Ausführungsform der vorliegenden Erfindung kann man Verbindung der allgemeinen Formel VI mit einem Diisocyanat, beispielsweise TMXDI (Tetramethylxylylendiisocyanat) umsetzen und erhält erfindungsgemäße Verbindung der allgemeinen Formel IV b, in der die Variablen wie vorstehend definiert sind.
In einer Ausführungsform der vorliegenden Erfindung kann man die Herstellung von erfindungsgemäßen Verbindungen der Formel IV b in Gegenwart eines Katalysators durchführen, beispielsweise in Gegenwart einer Zinn-organischen Verbindung, insbesondere In Gegenwart von DBTL (Di-n-butylzinndilaurat).In one embodiment of the present invention, the preparation of compounds of the formula IV b according to the invention can be carried out in the presence of a catalyst, for example in the presence of a tin-organic compound, in particular in the presence of DBTL (di-n-butyltin dilaurate).
In einer Ausführungsform der vorliegenden Erfindung kann man die Herstellung von erfindungsgemäßen Verbindungen der Formel IV b in Gegenwart eines Lösungsmittels durchführen. Geeignet sind beispielsweise cyclische und nichtcyclische Ether, beispielsweise THF, 1,4-Dioxan und Di-n-butylether, weiterhin Aceton und unpolare Lösungsmittel, beispielsweise Cyclohexan.In one embodiment of the present invention, it is possible to carry out the preparation of compounds of the formula IVb according to the invention in the presence of a solvent. Examples of suitable compounds are cyclic and noncyclic ethers, for example THF, 1,4-dioxane and di-n-butyl ether, furthermore acetone and nonpolar solvents, for example cyclohexane.
In einer Ausführungsform der vorliegenden Erfindung kann man die Herstellung von erfindungsgemäßen Verbindungen der Formel IV b bei einer Temperatur im Bereich von 20 bis 100 °C, bevorzugt 20 bis 80 °C durchführen.In one embodiment of the present invention, the preparation of compounds of the formula IV b according to the invention can be carried out at a temperature in the range from 20 to 100.degree. C., preferably from 20 to 80.degree.
In einer Ausführungsform der vorliegenden Erfindung kann man die Herstellung von erfindungsgemäßen Verbindungen der Formel IV b über eine Reaktionsdauer im Bereich von 1 bis 10 Stunden, bevorzugt 2 bis 5 Stunden durchführen.In one embodiment of the present invention, the preparation of compounds of the formula IV b according to the invention can be carried out over a reaction time in the range from 1 to 10 hours, preferably 2 to 5 hours.
Wünscht man solche erfindungsgemäße Verbindungen herzustellen, bei denen R1 Wasserstoff ist, so ist es bevorzugt, zunächst als R1 eine Schutzgruppe einzuführen, beispielsweise eine Acetatschutzgruppe, die man in einem späteren Reaktionsschritt abspaltet, beispielsweise unter sauren wässrigen Bedingungen.If it is desired to prepare such compounds according to the invention in which R 1 is hydrogen, it is preferable first to introduce a protective group as R 1 , for example an acetate protecting group, which is split off in a later reaction step, for example under acidic aqueous conditions.
Andere bevorzugte Schutzgruppen sind Acetal- und Ketalschutzgruppen, beispielsweise
Wünscht man auf Basis einer Acetal- oder Ketalschutzgruppe eine erfindungsgemäße Verbindung der allgemeinen Formel IV aufzubauen, so geht man vorzugsweise von einem acetalisierten oder ketalisierten Triol aus, beispielsweise von acetalisiertem oder ketalisiertem Glycerin oder acetalisiertem oder ketalisiertem Trimethylolpropan. Man setzt unter den vorstehend beschriebenen Bedingungen einmal oder mehrfach mit Epichlorhydrin um und erhält ein verzweigtes Molekül, das man mit beispielsweise Säurechlorid oder Säureanhydrid oder einem anderen geeigneten Derivat einer ethylenisch ungesättigten Carbonsäure zu Verbindung der allgemeinen Formel IV a oder mit einem geeigneten Diisocyanat zu Verbindung der allgemeinen Formel IV b umsetzen kann. Durch Hydrolyse unter schwach sauren Bedingungen kann man die Acetalgruppe bzw. Ketalgruppe abspalten, wenn es gewünscht ist, und erhält erfindungsgemäße Verbindungen mit R1 = Wasserstoff.If it is desired to synthesize a compound of the general formula IV based on an acetal or ketal protective group, preference is given to starting from an acetalated or ketalized triol, for example acetalated or ketalized glycerol or acetalated or ketalized trimethylolpropane. It is reacted under the conditions described above once or several times with epichlorohydrin and obtains a branched molecule, which is, for example, acid chloride or acid anhydride or other suitable derivative of an ethylenically unsaturated carboxylic acid to give compound of general formula IV or a suitable diisocyanate to compound of general formula IV b can implement. By hydrolysis under weakly acidic conditions, one can split off the acetal group or ketal group, if desired, and obtain compounds of the invention with R 1 = hydrogen.
Besonders bevorzugte Ketal-Schutzgruppe ist die Isopropyliden-Schutzgruppe.Particularly preferred ketal protecting group is the isopropylidene protecting group.
Natürlich ist es möglich, nach jedem der vorstehend genannten Arbeitsschritte eine oder mehrere Reinigungsoperationen durchzuführen. So ist es beispielsweise bevorzugt, entstandene Halogenide abzutrennen, beispielsweise durch Filtration. Weiterhin ist es bevorzugt, bei vermindertem Druck zu trocknen, beispielsweise um flüchtige Verunreinigungen abzutrennen.Of course, it is possible to perform one or more cleaning operations after each of the above-mentioned operations. For example, it is preferable to separate off any halides formed, for example by filtration. Furthermore, it is preferred to dry at reduced pressure, for example to separate off volatile impurities.
Ein weiterer Gegenstand der vorläufigen Erfindung ist ein Verfahren zur Herstellung von erfindungsgemäßen Copolymeren.Another object of the provisional invention is a process for the preparation of copolymers according to the invention.
Die erfindungsgemäße Herstellung von erfindungsgemäßen Copolymeren kann man beispielsweise so durchführen, dass man mit einem geeigneten Initiator eine vorzugsweise radikalische Copolymerisation von Verbindung der allgemeinen Formel IV a und/oder IV b sowie Comonomer (A) und Comonomer(en) (C) auslöst, gegebenenfalls in Gegenwart von mindestens einem Comonomer der allgemeinen Formel V a bis-V c,
- R2, R3
- gleich oder verschieden und gewählt aus C1-C6-Alkyl, bevorzugt n-C1-C4-Alkyl, besonders bevorzugt Methyl und insbesondere Wasserstoff,
- R4
- C1-C6-Alkyl, bevorzugt n-C1-C4-Alkyl, besonders bevorzugt Methyl, bevorzugt COOM und insbesondere Wasserstoff,
- M
- gewählt aus Ammonium, substituiert oder vorzugsweise unsubstituiert, Wasserstoff und Metallkationen, insbesondere Alkalimetallkationen oder einem halben Äquivalent Erdalkalimetallkationen.
- R 2 , R 3
- identical or different and selected from C 1 -C 6 -alkyl, preferably nC 1 -C 4 -alkyl, particularly preferably methyl and in particular hydrogen,
- R 4
- C 1 -C 6 -alkyl, preferably nC 1 -C 4 -alkyl, particularly preferably methyl, preferably COOM and in particular hydrogen,
- M
- selected from ammonium, substituted or preferably unsubstituted, hydrogen and metal cations, in particular alkali metal cations or half an equivalent of alkaline earth metal cations.
Geeignete Initiatoren sind insbesondere Radikalstarter, beispielsweise organische Peroxide, insbesondere organische Peroxide mit mindestens einer tert.-Butylgruppe oder mindestens einer tert.-Amylgruppe, und Azoverbindungen, beispielsweise Azobisisobutyronitril (AIBN). Auch Redoxinitiatoren sind geeignet, beispielsweise Kombinbationen aus Wasserstoffperoxid oder Natriumperoxodisulfat oder einem der vorstehend genannten Peroxide mit einem Reduktionsmittel. Als Reduktionsmittel sind beispielsweise geeignet: Ascorbinsäure, Weinsäure, Natriumbisulfit, Kaliumbisulfit, Fe(II)-Salze wie beispielsweise FeSO4 oder Alkalimetallsalze von Chelaten von Fe(II). Weiterhin sind anorganische Peroxide geeignet, beispielsweise Kaliumperoxodisulfat und Natriumperoxodisulfat.Suitable initiators are in particular radical initiators, for example organic peroxides, in particular organic peroxides having at least one tert-butyl group or at least one tert-amyl group, and azo compounds, for example azobisisobutyronitrile (AIBN). Also, redox initiators are suitable, for example Kombinbationen of hydrogen peroxide or sodium peroxodisulfate or one of the above mentioned peroxides with a reducing agent. Suitable reducing agents are, for example, ascorbic acid, tartaric acid, sodium bisulfite, potassium bisulfite, Fe (II) salts such as FeSO 4 or alkali metal salts of chelates of Fe (II). Furthermore, inorganic peroxides are suitable, for example potassium peroxodisulfate and sodium peroxodisulfate.
Die erfindungsgemäße Herstellung von erfindungsgemäßen Copolymeren durch Copolymerisation von Verbindung der allgemeinen Formel IV a und/oder IV b, im Rahmen der vorliegenden Erfindung auch erfindungsgemäße Copolymerisation genannt, kann man beispielsweise unter Verwendung von mindestens einem Lösungsmittel durchführen. Geeignete Lösungsmittel können beispielsweise sein: N,N-Dimethylformamid (DMF), Dioxan, Toluol oder unpolare Lösungsmittel wie beispielsweise Cyclohexan.The inventive production of copolymers according to the invention by copolymerization of compound of the general formula IV a and / or IV b, also called copolymerization according to the invention in the context of the present invention, can be carried out, for example, using at least one solvent. Suitable solvents may be, for example: N, N-dimethylformamide (DMF), dioxane, toluene or non-polar solvents such as cyclohexane.
In einer Ausführungsform der vorliegenden Erfindung ist Wasser ein geeignetes Lösungsmittel. Dies ist insbesondere dann der Fall, wenn man die erfindungsgemäße Copolymerisation mit anorganischem Peroxid zu starten wünscht.In one embodiment of the present invention, water is a suitable solvent. This is especially the case if one wishes to start the copolymerization according to the invention with inorganic peroxide.
In einer anderen Ausführungsform der vorliegenden Erfindung führt man die erfindungsgemäße Copolymerisation ohne Verwendung eines Lösungsmittels durch.In another embodiment of the present invention, the copolymerization according to the invention is carried out without the use of a solvent.
In einer Ausführungsform der vorliegenden Erfindung wählt man als Konzentration des bzw. der Comonomeren zu Beginn der erfindungsgemäßen Copolymerisation einen Bereich von 60 bis 95 Gew.-%, bevorzugt 70 bis 80 Gew.-% an Comonomer, bezogen auf sämtliche Comonomere. Man kann die erfindungsgemäße Copolymerisation auch als Massepolymerisation, also ohne Zugabe von Lösungsmittel, durchführen.In one embodiment of the present invention, the concentration of the comonomer (s) at the beginning of the copolymerization according to the invention is from 60 to 95% by weight, preferably from 70 to 80% by weight of comonomer, based on all comonomers. The copolymerization according to the invention can also be carried out as bulk polymerization, ie without addition of solvent.
In einer Ausführungsform der vorliegenden Erfindung führt man die erfindungsgemäße Copolymerisation als Emulsionspolymerisation durch.In one embodiment of the present invention, the copolymerization according to the invention is carried out as emulsion polymerization.
Die erfindungsgemäße Copolymerisation kann man als kontinuierliches Verfahren, als semikontinuierliches Verfahren oder in Form einer Batch-Copolymerisation durchführen.The copolymerization according to the invention can be carried out as a continuous process, as a semi-continuous process or in the form of a batch copolymerization.
In einer Ausführungsform der vorliegenden Erfindung führt man die erfindungsgemäße (Co)polymerisation bei Temperaturen im Bereich von 60 bis 90°C durch.In one embodiment of the present invention, the (co) polymerization according to the invention is carried out at temperatures in the range from 60 to 90.degree.
Durch die Ausübung des erfindungsgemäßen Verfahrens erhält man erfindungsgemäßes Copolymer.By practicing the process according to the invention, the copolymer according to the invention is obtained.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Verbindungen der allgemeinen Formel IV a
- R1
- verschieden oder vorzugsweise gleich und gewählt aus Wasserstoff oder bevorzugt C6-C30-Aryl, bevorzugt C6-C14-Aryl, insbesondere Phenyl; C7-C30-Aralkyl, bevorzugt Benzyl; C3-C10-Cycloalkyl, bevorzugt Cyclopentyl oder Cyclohexyl, und insbesondere C1-C30-Alkyl, bevorzugt C1-C20-Alkyl.
- A1
- verschieden oder vorzugsweise gleich und gewählt aus C6-C10-Arylen, vorzugsweise Phenylen, C7-C10-Aralkylen wie beispielsweise -CH(C6H5)- oder -CH2-CH(C6H5)-, und insbesondere aus C2-C10-Alkylen, substituiert oder vorzugsweise nicht substituiert, bevorzugt -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, ganz besonders bevorzugt -CH2-CH2-,
- n
- verschieden oder gleich und gewählt aus null bis 200, bevorzugt 1 bis 150, besonders bevorzugt 5 bis 50,
- m
- gewählt aus 1 bis 6, bevorzugt bis 4, besonders bevorzugt bis 2,
- R5
- gewählt aus Wasserstoff und Methyl,
- t
- gewählt aus null und eins.
- w
- gewählt aus null und eins,
- A2
- gewählt aus C1-C50-Alkylen, substituiert oder vorzugsweise nicht substituiert, wobei eine oder mehrere nicht-benachbarte CH2-Gruppen durch Sauerstoff ersetzt sein können. Beispiele für besonders geeignete Gruppen A2 sind C2-C10-Alkylen, bevorzugt -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, besonders bevorzugt -CH2-CH2-, weiterhin -CH2-CH2-O-, -CH(CH3)-CH2-O-, -CH2-CH(CH3)-O-, -[CH2-CH2-O]y-, -[CH(CH3)-CH2-O]y-, -[CH2-CH(CH3)-O-]y, wobei y eine ganze Zahl im Bereich von 2 bis 20, bevorzugt 2 bis 15 und insbesondere 3 bis 10 ist.
- R 1
- different or preferably identical and selected from hydrogen or preferably C 6 -C 30 -aryl, preferably C 6 -C 14 -aryl, in particular phenyl; C 7 -C 30 aralkyl, preferably benzyl; C 3 -C 10 -cycloalkyl, preferably cyclopentyl or cyclohexyl, and in particular C 1 -C 30 -alkyl, preferably C 1 -C 20 -alkyl.
- A 1
- different or preferably identical and selected from C 6 -C 10 -aryls, preferably phenylene, C 7 -C 10 -aralkylenes such as -CH (C 6 H 5 ) - or -CH 2 -CH (C 6 H 5 ) -, and in particular from C 2 -C 10 -alkylene, substituted or preferably unsubstituted, preferably -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 3 ) -, very particularly preferably -CH 2 -CH 2 -,
- n
- different or the same and selected from zero to 200, preferably from 1 to 150, particularly preferably from 5 to 50,
- m
- selected from 1 to 6, preferably up to 4, particularly preferred up to 2,
- R 5
- selected from hydrogen and methyl,
- t
- chosen from zero and one.
- w
- chosen from zero and one,
- A 2
- selected from C 1 -C 50 alkylene, substituted or preferably unsubstituted, wherein one or more non-adjacent CH 2 groups may be replaced by oxygen. Examples of particularly suitable groups A 2 are C 2 -C 10 -alkylene, preferably -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 3 ) -, particularly preferably - CH 2 -CH 2 -, furthermore -CH 2 -CH 2 -O-, -CH (CH 3 ) -CH 2 -O-, -CH 2 -CH (CH 3 ) -O-, - [CH 2 -CH 2 -O] y -, - [CH (CH 3 ) -CH 2 -O] y -, - [CH 2 -CH (CH 3 ) -O-] y , where y is an integer in the range of 2 to 20 , preferably 2 to 15 and in particular 3 to 10.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Verbindungen der allgemeinen Formel IV b
Dabei sind die Variablen wie vorstehend definiert:
- R1
- verschieden oder vorzugsweise gleich und gewählt aus Wasserstoff oder bevorzugt C6-C30-Aryl, bevorzugt C6-C14-Aryl, insbesondere Phenyl; C7-C30-Aralkyl, bevorzugt Benzyl; C3-C10-Cycloalkyl, bevorzugt Cyclopentyl oder Cyclohexyl, und insbesondere C1-C30-Alkyl, bevorzugt C1-C20-Alkyl;
- A1
- verschieden oder vorzugsweise gleich und gewählt aus C6-C10-Arylen, vorzugsweise Phenylen, C7-C10-Aralkylen wie beispielsweise -CH(C6H5)- oder -CH2-CH(C6H5)-, und insbesondere aus C2-C10-Alkylen, substituiert oder vorzugsweise nicht substituiert, bevorzugt -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, ganz besonders bevorzugt -CH2-CH2-,
- n
- verschieden oder gleich und gewählt aus null bis 200, bevorzugt 1 bis 150, besonders bevorzugt 5 bis 50,
- m
- gewählt aus 1 bis 6, bevorzugt bis 5, besonders bevorzugt 2 bis 4,
- R5
- gewählt aus Wasserstoff und Methyl.
- R 1
- different or preferably identical and selected from hydrogen or preferably C 6 -C 30 -aryl, preferably C 6 -C 14 -aryl, in particular phenyl; C 7 -C 30 aralkyl, preferably benzyl; C 3 -C 10 -cycloalkyl, preferably cyclopentyl or cyclohexyl, and especially C 1 -C 30 -alkyl, preferably C 1 -C 20 -alkyl;
- A 1
- different or preferably identical and selected from C 6 -C 10 -aryls, preferably phenylene, C 7 -C 10 -aralkylenes such as -CH (C 6 H 5 ) - or -CH 2 -CH (C 6 H 5 ) -, and in particular from C 2 -C 10 -alkylene, substituted or preferably unsubstituted, preferably -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 3 ) -, very particularly preferably -CH 2 -CH 2 -,
- n
- different or the same and selected from zero to 200, preferably from 1 to 150, particularly preferably from 5 to 50,
- m
- selected from 1 to 6, preferably to 5, particularly preferably 2 to 4,
- R 5
- selected from hydrogen and methyl.
Erfindungsgemäße Verbindungen der allgemeinen Formel IV a und IV b sind beispielsweise sehr gut geeignet, um erfindungsgemäße Verbindungen (B) herzustellen. Ihre Herstellung gelingt beispielsweise nach dem vorstehend beschriebenen Verfahren.For example, compounds of the general formula IVa and IVb according to the invention are very well suited for preparing compounds (B) according to the invention. Their preparation succeeds, for example, according to the method described above.
Die Erfindung wird durch Arbeitsbeispiele erläutert.The invention will be explained by working examples.
Allgemeine Vorbemerkungen: Die Darstellung der Verbindungen der Formel VI und IV erfolgte in Lösungsmitteln, die nach Standardmethoden getrocknet waren.
Die Bestimmung der Molekulargewichte erfolgte durch GPC in DMAC (N,N-Dimethylacetamid als Lösemittel), Standard: PMMA.
Unter Dioxan wird stets 1,4-Dioxan verstanden, wenn nicht anders angegeben.
Die (Co)polymerisationen wurden unter Schutzgasatmosphäre durchgeführt (getrockneter Stickstoff).
Angaben in % sind stets Gewichts-%, wenn nicht ausdrücklich anders angegeben.General Preliminary Remarks: The preparation of the compounds of the formula VI and IV was carried out in solvents which had been dried by standard methods.
The molecular weights were determined by GPC in DMAC (N, N-dimethylacetamide as solvent), standard: PMMA.
Dioxane is always understood to mean 1,4-dioxane, unless stated otherwise.
The (co) polymerizations were carried out under a protective gas atmosphere (dried nitrogen).
Figures in% are always% by weight unless otherwise stated.
In einem 2-Liter-Kolben mit Tropftrichter, Magnetrührer und Rückflusskühler wurde eine Lösung von 400 g (0,29 mol) Polyethylenglykolmonostearylether, CH3-(CH2)17-O-(CH2CH2-O)25H, in 1150 ml Dioxan vorgelegt. Unter Rühren gab man 25 g KOH-Plätzchen zu. Man erwärmte auf 105°C und gab dann 14 g (0,15 mol) Epichlorhydrin, gelöst in 50 ml Dioxan, über einen Zeitraum von 15 Minuten tropfenweise zu. Man rührte die inzwischen rotbraune Mischung über einen Zeitraum von 15 Stunden bei 105°C und kühlte dann auf Zimmertemperatur ab. Man filtrierte den entstandenen Niederschlag ab und destillierte das Dioxan bei 30 mbar ab. Man erhielt erfindungsgemäße Verbindung VI.1, ein zähes hellbraunes Öl, das durch MS (Maldi TOF) und durch GPC charakterisiert wurde. Mn: 3200 g/mol, Mw: 4200 g/mol.
In einem 2-Liter-Kolben mit Tropftrichter, Magnetrührer und Rückflusskühler wurde eine Lösung von 400 g (0,53 mol) Polyethylenglykol-monomethylether (Mw = 750 g/mol, n = 16) in 1150 ml Dioxan vorgelegt. Unter Rühren gab man 30 g KOH-Plätzchen zu. Man erwärmte auf 105°C und gab dann 25 g (0,26 mol) Epichlorhydrin, gelöst in 50 ml Dioxan, über einen Zeitraum von 30 Minuten tropfenweise zu. Man rührte die so erhältliche Mischung über einen Zeitraum von 15 Stunden bei 105°C und kühlte dann auf Zimmertemperatur ab. Man filtrierte den entstandenen Niederschlag ab und destillierte das Dioxan bei 30 mbar ab. Man erhielt erfindungsgemäße Verbindung VI.2, ein zähes gelbliches Öl, das durch MS (Maldi TOF) und durch GPC charakterisiert wurde. Mn = 1800 g/mol, Mw = 2400 g/mol.
In einem 2-Liter-Kolben mit Tropftrichter, Magnetrührer und Rückflusskühler wurde eine Lösung von 365 g (1,04 mol) H-(OCH2CH2)7-O-n-C12H25 (Mw = 490 g/mol, n = 7) in 1600 ml Dioxan vorgelegt. Unter Rühren gab man 67 g KOH-Plätzchen zu. Man erwärmte auf 105°C und gab dann 35 g (0,37 mol) Epichlorhydrin, gelöst in 100 ml Dioxan, über einen Zeitraum von 30 Minuten tropfenweise zu. Man rührte die so erhältliche Mischung über einen Zeitraum von 15 Stunden bei 105°C und kühlte dann auf Zimmertemperatur ab. Man filtrierte den entstandenen Niederschlag ab und destillierte das Dioxan bei 30 mbar ab. Man erhielt erfindungsgemäße Verbindung VI.3, ein gelbliches Öl, das durch MS (Maldi TOF) und durch GPC charakterisiert wurde. Mn = 1470 g/mol, Mw = 1940 g/mol.
In einem 4-Liter-Kolben mit Tropftrichter, Magnetrührer und Rückflusskühler wurde eine Lösung von 700 g (0,93 mol) H-(OCH2CH2)16-OCH3 (Mw = 750 g/mol, n = 16) in 1600 ml Dioxan vorgelegt. Unter Rühren gab man 224 g KOH-Plätzchen zu. Man erwärmte auf 105°C und gab dann 43 g (0,45 mol) Epichlorhydrin, gelöst in 175 ml Dioxan, über einen Zeitraum von 30 Minuten tropfenweise zu. Man rührte die so erhältliche Mischung über einen Zeitraum von 2 Stunden und gab dann tropfenweise weitere 21 g (0,23 mol) Epichlorhydrin in 100 ml Dioxan über einen Zeitraum von 30 Minuten zu. Man rührte die so erhältliche Mischung über einen Zeitraum von 2 Stunden und gab dann tropfenweise weitere 10,8 g (0,115 mol) Epichlorhydrin in 50 ml Dioxan über einen Zeitraum von 15 Minuten zu. Man rührte 15 Stunden bei 105°C und kühlte dann auf Zimmertemperatur ab. Man filtrierte den entstandenen Niederschlag ab und destillierte das Dioxan bei 30 mbar ab. Man erhielt erfindungsgemäße Verbindung VI.4, ein gelbliches Öl, das durch MS (Maldi TOF) und durch GPC charakterisiert wurde. Mn = 2400 g/mol, Mw = 3100 g/mol.
In einem 2000-ml-Kolben, der mit Tropftrichter und Magnetrührer ausgestattet war, wurde eine Lösung von 200 g Verbindung VI.1 in 800 ml THF vorgelegt. Man rührte 20 Minuten bei Zimmertemperatur und gab 50 mg para-N,N-Dimethylaminopyridin zu. Danach gab man über einen Zeitraum von 15 Minuten eine Lösung von 15,5 g Methacrylsäureanhydrid, gelöst in 50 ml THF, tropfenweise zu. Man beobachtete die Bildung einer geringen Menge an Niederschlag. Man rührte noch 3 Stunden bei Zimmertemperatur, trennte den Niederschlag durch Filtration ab und destillierte dann das THF bei Zimmertemperatur und verringertem Druck ab. Man erhielt erfindungsgemäße Verbindung IV.1 als braunes Öl, welche durch MALDI-TOF und GPC charakterisiert wurde.In a 2000 ml flask equipped with dropping funnel and magnetic stirrer, a solution of 200 g of compound VI.1 in 800 ml of THF was placed. The mixture was stirred at room temperature for 20 minutes and 50 mg of para-N, N-dimethylaminopyridine were added. Thereafter, a solution of 15.5 g of methacrylic anhydride dissolved in 50 ml of THF was added dropwise over a period of 15 minutes. The formation of a small amount of precipitate was observed. The mixture was stirred for 3 hours at room temperature, the precipitate was separated by filtration and then distilled the THF at room temperature and reduced pressure. Compound IV.1 according to the invention was obtained as a brown oil which was characterized by MALDI-TOF and GPC.
In einem 2-I-Kolben, der mit Tropftrichter und Magnetrührer ausgestattet war, wurde eine Lösung von 200 g Verbindung VI.2 in 800 ml THF vorgelegt. Man rührte 20 Minuten bei Zimmertemperatur und gab 50 mg para-N,N-Dimethylaminopyridin zu. Danach gab man über einen Zeitraum von 15 Minuten eine Lösung von 9 g Methacrylsäureanhydrid, gelöst in 50 ml THF, tropfenweise zu. Man beobachtete die Bildung einer geringen Menge an Niederschlag. Man rührte noch 3 Stunden bei Zimmertemperatur, trennte den Niederschlag durch Filtration ab und destillierte dann das THF bei Zimmertemperatur und verringertem Druck ab. Man erhielt erfindungsgemäße Verbindung IV.2 als braunen Feststoff.In a 2 l flask equipped with dropping funnel and magnetic stirrer, a solution of 200 g of compound VI.2 in 800 ml of THF was initially charged. The mixture was stirred at room temperature for 20 minutes and 50 mg of para-N, N-dimethylaminopyridine were added. Thereafter, over a period of 15 minutes, a solution of 9 g of methacrylic anhydride dissolved in 50 ml of THF was added dropwise. The formation of a small amount of precipitate was observed. The mixture was stirred for 3 hours at room temperature, the precipitate was separated by filtration and then distilled the THF at room temperature and reduced pressure. Compound IV.2 according to the invention was obtained as a brown solid.
In einem 1-I-Kolben, der mit Tropftrichter und Magnetrührer ausgestattet war, wurde eine Lösung von 200 g Verbindung VI.3 in 600 ml THF vorgelegt. Man rührte 20 Minuten bei Zimmertemperatur und gab 50 mg para-N,N-Dimethylaminopyridin zu. Danach gab man über einen Zeitraum von 20 Minuten eine Lösung von 19 g Methacrylsäureanhydrid, gelöst in 50 ml THF, tropfenweise zu. Man rührte noch 3 Stunden bei Zimmertemperatur, filtrierte und destillierte dann das THF bei Zimmertemperatur und verringertem Druck ab. Man erhielt erfindungsgemäße Verbindung IV.3, die durch MALDI-TOF charakterisiert wurde.In a 1 l flask equipped with dropping funnel and magnetic stirrer, a solution of 200 g of compound VI.3 in 600 ml of THF was introduced. The mixture was stirred at room temperature for 20 minutes and 50 mg of para-N, N-dimethylaminopyridine were added. Thereafter, a solution of 19 g of methacrylic anhydride dissolved in 50 ml of THF was added dropwise over a period of 20 minutes. The mixture was stirred for 3 hours at room temperature, filtered and then distilled from the THF at room temperature and reduced pressure. Compound IV.3 according to the invention was obtained, which was characterized by MALDI-TOF.
In einem 2,5-I-Autoklaven wurden 1000 g erfindungsgemäße Verbindung VI.4 und 10 g KOH vorgelegt, mit Stickstoff (2 bar) intertisiert und danach auf 120°C erhitzt. Danach wurde Acetylen mit einem Druck von 20 bar aufgepresst und die Reaktionsmischung bei 120°C und 20 bar gerührt, bis insgesamt 85 l Acetylen aufgenommen waren. Danach wurde auf Raumtemperatur abgekühlt, entspannt und der Rückstand nach Erwärmen auf 60°C für 3 h unter Rühren entgast und dann dem Autoklav entnommen. Verbindung IV.4 wurde durch 1H-NMR-Spektroskopie charakterisiert.
Aus denen erfindungsgemäßen Verbindungen IV.1 bis IV.3 wurden dispergierte erfindungsgemäße Copolymere hergestellt. Für die Anwendung dieser dispergierten erfindungsgemäßen Copolymere in Wasch- und Reinigungsmitteln sowie für Kosmetikartikel wird die Erfindung durch die folgenden Anwendungsbeispiele näher veranschaulicht.From inventive compounds IV.1 to IV.3 dispersed copolymers of the invention were prepared. For the application of these dispersed copolymers of the invention in detergents and cleaners as well as for cosmetics, the invention is illustrated in more detail by the following application examples.
Man stellte Emulsion E.3.1 her, bestehend aus
220 g vollständig entsalztes Wasser (VE-Wasser)
137,3 g Methacrylsäure (A.1)
155,3 g Ethylacrylat (C.1)
164,4 g n-Butylacrylat (C.2)
12,5 g erfindungsgemäße Verbindung IV.1 (B.1)
12,32 g einer 28 Gew.-% wässrigen Lösung von Laurylethersulfat als Emulgator E-mul.1.
8,63 g einer 0,4% wässrigen Ascorbinsäure-LösungEmulsion E.3.1 was prepared, consisting of
220 g of completely desalinated water (demineralised water)
137.3 g of methacrylic acid (A.1)
155.3 g of ethyl acrylate (C.1)
164.4 g of n-butyl acrylate (C.2)
12.5 g of compound IV.1 (B.1) according to the invention
12.32 g of a 28 wt .-% aqueous solution of lauryl ether sulfate as emulsifier E-mul.1.
8.63 g of a 0.4% aqueous ascorbic acid solution
In einer Rührapparatur, bestehend aus einem 2-Liter-HWS-Gefäß mit Ankerrührer (175 Upm), Rückflusskühler, Innenthermofühler und Dosierstation, wurden als Vorlage 675,9 g entsalztes Wasser (VE-Wasser), 0,2 g einer 4 Gew.-% [FeK2(EDTA)]-Lösung (EDTA = Ethylendiamintetraacetat) und 12,3 g einer 28 Gew.-% wässrigen Lösung von Laurylethersulfat) miteinander vermischt. Man erwärmte auf 75°C.In a stirring apparatus, consisting of a 2-liter HWS vessel with anchor stirrer (175 rpm), reflux condenser, internal thermocouple and dosing, were used as a template 675.9 g of deionized water (deionized water), 0.2 g of a 4 wt. -% [FeK 2 (EDTA)] - solution (EDTA = ethylenediaminetetraacetate) and 12.3 g of a 28 wt .-% aqueous solution of lauryl ether sulfate) mixed together. The mixture was heated to 75 ° C.
Danach gab man 9,2 g einer 1 Gew.-% wässrigen Wasserstoffperoxid-Lösung zu. Danach wurden unter weiterem Rühren bei 75 °C 50% der Emulsion E.3.1 zudosiert. Anschließend wurde die Reaktionsmischung auf 65°C abgekühlt. Bei 65°C wurde übrige Emulsion E.3.1 zudosiert. Man rührte bei 65°C über einen Zeitraum von 23 Minuten. Danach wurden 6,6 g einer 7 Gew.-% wässrigen Na2S2O8-Lösung und 86,2 g einer 0,4%igen Ascorbinsäure-Lösung zudosiert. Danach wurde die Reaktionsmischung auf Raumtemperatur abgekühlt. Man erhielt eine wässrige Dispersion von erfindungsgemäßem Copolymer CP.1, die 31 % Feststoffgehalt aufwies.Thereafter, 9.2 g of a 1 wt .-% aqueous hydrogen peroxide solution was added. Thereafter, with further stirring at 75 ° C, 50% of the emulsion E.3.1 was added. Subsequently, the reaction mixture was cooled to 65 ° C. At 65 ° C remaining emulsion E.3.1 was added. The mixture was stirred at 65 ° C over a period of 23 minutes. Thereafter, 6.6 g of a 7 wt .-% aqueous Na 2 S 2 O 8 solution and 86.2 g of a 0.4% ascorbic acid solution were added. Thereafter, the reaction mixture was cooled to room temperature. This gave an aqueous dispersion of inventive copolymer CP.1, which had 31% solids content.
Die Daten zu den erfindungsgemäßen Copolymeren CP.2 bis CP.10 finden sich in Tabelle 1.
Zur Herstellung von CP.2 bis CP.10 wurde wie unter III.1 vorgegangen, jedoch wurden die Anteile an Comonomeren variiert. Außerdem wurde Art und Menge an Emulgator gemäß Tabelle 1 eingesetzt.
Unter Emulgator Emul.2 ist Sulfobernsteinsäure-di-2-ethylhexylester-Na-Salz zu verstehen.
Die Mengenangaben für die Einsatzstoffe sind in Gewichtsteilen pro 100 reaktive Monomerteile (parts per hundred monomers; pphm) angegeben. Zur Charakterisierung der Dispersion wurden folgende Werte gemessen:
- Feststoffgehalt, "Feststoff": Die betreffende Dispersion wurde 30 min bei 140 °C getrocknet und der Feststoffgehalt in Prozent aus dem Verhältnis Trockenrückstand zu Einwaage bestimmt.
For the preparation of CP.2 to CP.10, the procedure was as in III.1, but the proportions of comonomers were varied. In addition, type and amount of emulsifier according to Table 1 was used.
Emulsifier Emul.2 is sulfosuccinic acid di-2-ethylhexyl ester Na salt.
The amounts given for the starting materials are given in parts by weight per 100 parts by parts monomer (pphm). To characterize the dispersion, the following values were measured:
- Solids content, "solid": The dispersion in question was dried for 30 minutes at 140 ° C. and the solids content in percent determined from the ratio of dry residue to weight.
Teilchendurchmesser: Die betreffende Dispersion wurde mit Wasser auf 0,01 % verdünnt und die Teilchendurchmesser über Lichtstreuung im "High Performance Particle Sizer 5001" (HPPS) von der Firma Malvern Instruments gemessen.Particle diameter: The dispersion in question was diluted to 0.01% with water and the particle diameters were measured by light scattering in the "High Performance Particle Sizer 5001" (HPPS) from Malvern Instruments.
LD-Wert: Die betreffende Dispersion wurde mit Wasser auf 0,01 % verdünnt und die Lichtdurchlässigkeit (LD) der Dispersion im Vergleich zu reinem Wasser als Maß für den Teilchendurchmesser optisch im Hach DR/2010 gemessen.
Zur Anwendungsprüfung wurden erfindungsgemäße Copolymere in Stammformulierungen für Flüssigwaschmittel gemäß Tabelle 2 eingerührt und die verdickende Wirkung getestet. Die Stammformulierungen wurden aus den folgenden Stammformulierungen ausgewählt.For application testing, copolymers according to the invention were stirred into stock formulations for liquid detergents according to Table 2 and the thickening effect was tested. The stock formulations were selected from the following stock formulations.
Man vermischte miteinander:
- 13,0 g para-n-C10-C13-Alkyl-C6H4-SO3H,
- 7,5 g CH3(CH2)11-(O-CH2CH2)7-OH
- 8,5 g Kokosfettsäure (Fettsäuregemisch)
- 4,4 g KOH
- 3,0 g Natriumcitrat-dihydrat
- 8,0 g 1,2-Propylenglykol
- 2,0 g Ethanol
- und füllte mit Wasser auf 90 g auf.
- 13.0 g of para-nC 10 -C 13 -alkyl-C 6 H 4 -SO 3 H,
- 7.5 g of CH 3 (CH 2 ) 11 - (O-CH 2 CH 2 ) 7 -OH
- 8.5 g of coconut fatty acid (fatty acid mixture)
- 4.4 g KOH
- 3.0 g of sodium citrate dihydrate
- 8.0 g of 1,2-propylene glycol
- 2.0 g of ethanol
- and filled up with water to 90 g.
Man vermischte miteinander:
- 17,9 g para-n-C10-C13-Alkyl-C6H4-SO3H
- 20,0 g CH3(CH2)11-(O-CH2CH2)7-OH
- 8,5 g Kokosfettsäure (Fettsäuregemisch)
- 5,0 g KOH
- 3,0 g Natriumcitrat-dihydrat
- 8,0 g 1,2-Propylenglykol
- 2,0 g Ethanol
- und füllte mit Wasser auf 90 g auf.
- 17.9 g of para-nC 10 -C 13 -alkyl-C 6 H 4 -SO 3 H
- 20.0 g of CH 3 (CH 2 ) 11 - (O-CH 2 CH 2 ) 7 -OH
- 8.5 g of coconut fatty acid (fatty acid mixture)
- 5.0 g KOH
- 3.0 g of sodium citrate dihydrate
- 8.0 g of 1,2-propylene glycol
- 2.0 g of ethanol
- and filled up with water to 90 g.
Man vermischte miteinander:
- 13,4 g para-n-C10-C13-Alkyl-C6H4-S03H
- 10,0 g CH3(CH2)11-O-CH2CH2)7OH
- 8,5 g Kokosfettsäure (Fettsäuregemisch)
- 4,4 g KOH
- 3,0 g Natriumcitrat-dihydrat
- 8,0 g 1,2-Propylenglykol
- 2,0 g Ethanol
- und füllte mit Wasser auf 90 g auf.
- 13.4 g of para-nC 10 -C 13 -alkyl-C 6 H 4 -SO 3 H
- 10.0 g of CH 3 (CH 2 ) 11 -O-CH 2 CH 2 ) 7 OH
- 8.5 g of coconut fatty acid (fatty acid mixture)
- 4.4 g KOH
- 3.0 g of sodium citrate dihydrate
- 8.0 g of 1,2-propylene glycol
- 2.0 g of ethanol
- and filled up with water to 90 g.
Man vermischte 90 g Stammformulierung, wässrige Dispersion aus erfindungsgemäßem Copolymer und Wasser, so dass erfindungsgemäße Flüssigwaschmittel PWM.1 bis FWM.7 gemäß Tabelle 2 resultierten. Man ließ die erfindungsgemäßen Flüssigwaschmittel mindestens 5 Stunden bei Raumtemperatur ruhen und testete dann die anwendungstechnischen Eigenschaften. Die Resultate sind in Tabelle 2 zusammengefasst.90 g of the parent formulation, aqueous dispersion of copolymer according to the invention and water were mixed, so that liquid detergents PWM.1 to FWM.7 according to the invention according to Table 2 resulted. The liquid detergents according to the invention were allowed to rest for at least 5 hours at room temperature and then tested the performance properties. The results are summarized in Table 2.
Als Referenzformulierung wurde jeweils die betreffende Stammformulierung mit Wasser auf 100 g verdünnt.
Die Viskosität wurde unter Berücksichtigung der Vorschriften nach DIN 51550, DIN 53018, DIN 53019 mit dem Brookfield Viskosimeter Modell RV-03 bei einer Drehzahl von 20 Umdrehungen pro Minute mit der Spindel Nr. 62 bei 20 °C gemessen. Die Viskosität der unverdickten Referenzformulierungen ist in Tab. 1 den Vergleichsbeispiel 1 bis 3 zu entnehmen.The viscosity was measured taking into account the requirements of DIN 51550, DIN 53018, DIN 53019 with the Brookfield model RV-03 viscometer at a speed of 20 revolutions per minute with spindle no. 62 at 20 ° C. The viscosity of the non-thickened reference formulations can be seen in Tab. 1 Comparative Examples 1 to 3.
Zur Quantifizierung der Transparenz der erfindungsgemäßen Flüssigwaschmittel wurde die Transmission in % bei 440 nm bei 23 °C mit einem LICO 200 der Fa. Dr. Lange gemessen. Die Transmission der unverdickten Referenzformulierung und der erfindungsgemäßen Flüssigwaschmittel lagen im gleichen Bereich zwischen 97 und 100%. Durch Zugabe von erfindungsgemäßen Copolymeren wurde im erfindungsgemäßen Flüssigwaschmittel keine Trübung verursacht.To quantify the transparency of the liquid detergents according to the invention, the transmission in% at 440 nm at 23 ° C with a LICO 200 Fa. Long measured. The transmission of the non-thickened reference formulation and the liquid detergents according to the invention were in the same range between 97 and 100%. Addition of copolymers according to the invention caused no haze in the liquid detergent according to the invention.
Claims (14)
- A copolymer comprising as comonomers in copolymerized form(A) at least one ethylenically unsaturated mono- or dicarboxylic acid,(B) at least one ethylenically unsaturated compound which has at least one structural unit of the general formula I per molecule:R1 is different or identical and selected from hydrogen, C1-C30-alkyl, C3-C10-cycloalkyl, C6-C30-aryl and C7-C30-aralkyl,A1 is different or identical and selected from C2-C10-alkylene, C6-C10-arylene and C7-C10-aralkylene,n is different or identical and selected from zero to 200,m is different or identical and selected from 1 to 6, (C) at least one further comonomer.
- The copolymer according to claim 1, which has at least one structural unit of the general formula IIR2, R3 are identical or different and selected from C1-C6-alkyl and hydrogen,R4 is C1-C6-alkyl, COOM or hydrogen,M is selected from ammonium, substituted or unsubstituted, hydrogen and metal cations.
- The copolymer according to claim 1 or 2, wherein compound (B) has a molecular weight Mw in the range from 200 to 100 000 g/mol.
- The copolymer according to any one of claims 1 to 3, wherein compound (B) has a K value in accordance with Fikentscher in the range from 8 to 40, measured in water/THF mixtures.
- The copolymer according to any one of claims 1 to 4, wherein the molar ratio of structural units of the formula I to structural units of the formula II is in the range from 0.01 to 10.
- The copolymer according to any one of claims 1 to 5, wherein at least one structural unit of the general formula I is bonded to the basic backbone of said copolymer via a group of the formula III aX is selected from a single bond, oxygen and N-H,t is selected from zero and one,w is selected from zero and one,A2 is selected from C1-C50-alkylene, substituted or unsubstituted, where one or more nonadjacent CH2 groups may be replaced by oxygen.
- The use of copolymers according to any one of claims 1 to 6 as thickeners.
- A detergent or cleaner or cosmetic preparation comprising at least one copolymer according to any one of claims 1 to 6.
- A compound (B), which has at least one structural unit of the general formula I per molecule:R1 is different or identical and selected from hydrogen, C1-C30-alkyl, C3-C10-cycloalkyl, C6-C30-aryl and C7-C30-aralkyl,A1 is different or identical and selected from C2-C10-alkylene, C6-C10-arylene and C7-C10-aralkylene,n is different or identical and selected from zero to 200,m is different or identical and selected from 1 to 6.
- The compound (B) according to claim 9, which has a molecular weight Mw in the range from 200 to 100 000 g/mol.
- The compound (B) according to claim 9 or 10, which comprises, in copolymerized form, at least one comonomer of the general formula IV a or IV b,R1 is different or identical and selected from hydrogen, C1-C30-alkyl, C3-C10-cycloalkyl, C6-C30-aryl and C7-C30-aralkyl,A1 is different or identical and selected from C2-C10-alkylene, C6-C10-arylene and C7-C10-aralkylene,n is different or identical and selected from zero to 200,m is different or identical and selected from 1 to 6,R5 is selected from hydrogen and methyl,t is selected from zero and one,w is selected from zero and one,X is selected from a single bond, oxygen and N-H,A2 is selected from C1-C50-alkylene, substituted or unsubstituted, where one or more nonadjacent CH2 groups may be replaced by oxygen.
- A method of preparing (co)polymers according to any one of claims 1 to 6, wherein at least one (co)monomer of the general formula IV a or IV bR2, R3 are identical or different and selected from C1-C6-alkyl and hydrogen,R4 is C1-C6-alkyl, COOM or hydrogen,M is selected from ammonium, substituted or unsubstituted, hydrogen and metal cations,R5 is selected from hydrogen and methyl,t is selected from zero and one,w is selected from zero and one,X is selected from a single bond, oxygen and N-H,A2 is selected from C1-C50-alkylene, substituted or unsubstituted, where one or more nonadjacent CH2 groups may be replaced by oxygen.
- A compound of the general formula IV aR1 is different or identical and selected from hydrogen, C1-C30-alkyl, C3-C10-cycloalkyl, C6-C30-aryl and C7-C30-aralkyl,A1 is different or identical and selected from C2-C10-alkylene, C6-C10-arylene and C7-C10-aralkylene,n is different or identical and selected from zero to 200,m is different or identical and selected from 1 to 6,t is selected from zero and one,w is selected from zero and one,X is selected from a single bond, oxygen and N-H,A2 is selected from C1-C50-alkylene, substituted or unsubstituted, where one or more nonadjacent CH2 groups may be replaced by oxygen,R5 is selected from hydrogen and methyl.
- A compound of the general formula IV bR1 is different or identical and selected from hydrogen, C1-C30-alkyl, C3-C10-cycloalkyl, C6-C30-aryl and C7-C30-aralkyl,A1 is different or identical and selected from C2-C10-alkylene, C6-C10-arylene and C7-C10-aralkylene,n is different or identical and selected from zero to 200,m is different or identical and selected from 1 to 6,R5 is selected from hydrogen and methyl.
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EP10730180.6A EP2454296B1 (en) | 2009-07-15 | 2010-07-09 | Copolymers, their use as thickeners and method for producing the same |
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EP10730180.6A EP2454296B1 (en) | 2009-07-15 | 2010-07-09 | Copolymers, their use as thickeners and method for producing the same |
PCT/EP2010/059848 WO2011006838A2 (en) | 2009-07-15 | 2010-07-09 | Copolymers, their use as thickeners and method for producing the same |
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US (1) | US8492497B2 (en) |
EP (1) | EP2454296B1 (en) |
JP (1) | JP2012532975A (en) |
CN (1) | CN102471417B (en) |
ES (1) | ES2561844T3 (en) |
WO (1) | WO2011006838A2 (en) |
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EP2534234B1 (en) | 2010-02-12 | 2015-01-14 | Basf Se | Use of a copolymer as a thickener in liquid detergents having lower graying tendency |
US8530567B2 (en) * | 2010-02-18 | 2013-09-10 | Basf Se | Polymer dispersion which comprises a highly branched polycarbonate having unsaturated fatty acid groups |
CA2810099A1 (en) * | 2010-09-01 | 2012-03-08 | Basf Se | Associative thickener for aqueous preparations |
CN103189409B (en) | 2010-09-01 | 2015-11-25 | 巴斯夫欧洲公司 | For the amphiphile of solubilising microsolubility activeconstituents |
US8987357B2 (en) | 2011-05-27 | 2015-03-24 | Basf Se | Thermoplastic molding composition |
US10402890B2 (en) * | 2012-01-09 | 2019-09-03 | Packsize Llc | Box-last packaging system, method, and computer program product |
EP2774899A1 (en) * | 2013-03-06 | 2014-09-10 | Construction Research & Technology GmbH | Polycarboxylate ether with branched side chains |
US9126866B2 (en) * | 2013-03-06 | 2015-09-08 | Construction Research & Technology Gmbh | Polycarboxylate ethers with branched side chains |
EP2876128A1 (en) | 2013-11-25 | 2015-05-27 | Basf Se | Process for purifying water-soluble highly branched polyethers |
EP3137535B1 (en) | 2014-04-30 | 2018-06-13 | Basf Se | Mixed alkyl terminated polyether dendrons |
EP3421442B1 (en) | 2017-06-28 | 2020-08-05 | Construction Research & Technology GmbH | Dispersant for inorganic particles |
CN107626258B (en) * | 2017-10-23 | 2019-07-02 | 安徽工业大学 | A kind of synthetic method of carbon quantum dot quaternary cationics |
EP3828153A1 (en) * | 2019-11-29 | 2021-06-02 | Sika Technology Ag | Branched copolymers as dispersants for mineral binders |
EP3828154A1 (en) * | 2019-11-29 | 2021-06-02 | Sika Technology Ag | Branched copolymers as additives for reducing the viscosity of mineral binder compositions |
FR3104166B1 (en) * | 2019-12-09 | 2021-12-10 | Soc Dexploitation De Produits Pour Les Industries Chimiques Seppic | Detergent composition comprising an inverse latex combining a particular sequestering agent and a polyelectrolyte comprising a weak acid function |
CN115991846B (en) * | 2023-02-14 | 2023-07-14 | 重庆市泓择石油科技有限公司 | Clean residue-free acid liquor thickener and preparation method thereof |
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US362944A (en) * | 1887-05-17 | Spindle-support for spinning-machines | ||
US396416A (en) * | 1889-01-22 | mount | ||
JPS5918338B2 (en) * | 1981-10-30 | 1984-04-26 | 株式会社日本触媒 | cement dispersant |
JP2508804B2 (en) * | 1988-06-11 | 1996-06-19 | 日本油脂株式会社 | Solid cleaning agent for flush toilet |
AU8130598A (en) | 1997-07-14 | 1999-02-10 | Citizen Watch Co. Ltd. | Liquid crystal display |
DE59807982D1 (en) | 1997-07-30 | 2003-05-22 | Basf Ag | SOLID TEXTILE DETERGENT FORMULATION CONTAINING GLYCIN-N, N-DIACETIC ACID DERIVATIVES |
AU4682899A (en) * | 1998-06-15 | 2000-01-05 | Union Carbide Chemicals & Plastics Technology Corporation | Alkali soluble latex thickeners |
WO2000054361A1 (en) * | 1999-03-10 | 2000-09-14 | Daiso Co., Ltd. | Photoelectric conversion devices made by using ethereal electrolytes |
JP2000273794A (en) * | 1999-03-24 | 2000-10-03 | Dai Ichi Kogyo Seiyaku Co Ltd | Humectant for paper coating agent |
JP2001243987A (en) * | 2000-03-01 | 2001-09-07 | Daiso Co Ltd | Ether compound electrolyte battery |
US6569976B2 (en) * | 2000-05-30 | 2003-05-27 | Rohm And Haas Company | Amphiphilic polymer composition |
BRPI0416388B1 (en) * | 2003-11-20 | 2016-03-29 | Basf Ag | water soluble copolymer, use thereof, washing agent formulation, and washing liquid and solid formulations |
JP2006124210A (en) * | 2004-10-27 | 2006-05-18 | Sanyo Chem Ind Ltd | Additive for cement composition |
JP2009001776A (en) * | 2007-06-11 | 2009-01-08 | Rohm & Haas Co | Aqueous emulsion polymer associative thickener |
JP2009029847A (en) * | 2007-07-24 | 2009-02-12 | Isp Japan Kk | Thickener and cosmetics using the same |
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- 2010-07-09 CN CN201080031824.5A patent/CN102471417B/en active Active
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ES2561844T3 (en) | 2016-03-01 |
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CN102471417A (en) | 2012-05-23 |
US20110015361A1 (en) | 2011-01-20 |
JP2012532975A (en) | 2012-12-20 |
EP2454296A2 (en) | 2012-05-23 |
WO2011006838A3 (en) | 2011-05-26 |
US8492497B2 (en) | 2013-07-23 |
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